Solid catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer

ABSTRACT

A solid catalyst component for olefin polymerization in which the molar ratio of residual alkoxy groups to supported titanium is 0.60 or less is obtained by reacting the following compound (a1) with the following compound (b1) at a hydroxyl group/magnesium molar ratio of 1.0 or more, reacting the reaction mixture with the following compound (c1) at a halogen/magnesium molar ratio of 0.20 or more, reacting the resultant reaction mixture with the following compounds (d1) and (e) at a temperature of 120° C. or higher but 150° C. or lower, washing the reaction mixture with an inert solvent, reacting the reaction mixture with the following compound (e) again at the above temperature and washing the reaction mixture with an inert solvent, whereby there can be provided the solid catalyst component for olefin polymerization and a catalyst for olefin polymerization which have high polymerization activity and give an olefin polymer having a less residual C1 content and being excellent in stereoregularity and powder form and a process for producing an olefin polymer, (a1) an oxide of at least one element that is selected from Group II to Group IV elements and which supports an alcohol-free halogen-containing magnesium compound, (b1) an alcohol, (c1) a halogen-containing silicon compound, (d1) an electron-donating compound, and (e) a halogen-containing titanium compound.

TECHNICAL FIELD

The present invention relates to a solid catalyst component for olefinpolymerization for producing an α-olefin homopolymer or copolymer, acatalyst for olefin polymerization and a process for producing an olefinpolymer.

TECHNICAL BACKGROUND

Generally, an olefin polymer is produced by polymerization in thepresence of a Ziegler-Natta catalyst containing a titanium compound andan organic aluminum compound. For example, in the production of apolypropylene that is one of olefin polymers, an isotactic polypropyleneis obtained mainly in the presence of a catalyst containing a solidcatalyst component formed mainly from titanium, magnesium, chlorine andan electron-donating compound and containing an organic aluminumcompound as a co-catalyst component and an organosilicon compound havingan alkoxy group as a stereoregularity improver. Attempts are presentlymade to attain an improvement in the catalytic activity duringpolymerization, an improvement in stereoregularity of an olefin polymer,an improvement in the form of a polymer powder for stable production ofan olefin polymer and a reduction in residual C1 in the polymer.

When the above residual C1 in a polymer is large in amount, for example,the C1 corrodes a mold for injection molding, a polymer absorbs waterduring the production of a biaxially oriented film or its spinning tocause foaming, or a foreign matter containing an additive is formed,which makes high-speed molding difficult, so that it is a big issue todecrease the amount of residual C1 in a polymer.

As means for overcoming the problem of residual C1 in a polymer, first,it is general practice to employ a method in which a catalyst isimproved in activity. In the second place, it is also general practiceto employ a method in which a non-organic material such as silica isallowed to support a magnesium compound to substantially decrease amagnesium chloride content, i.e., a C1 content in a catalyst.

For example, there is known a method in which silica, butyl octylmagnesium and hydrogen chloride gas are brought into contact to form amagnesium-chloride-supporting silica support, the thus-prepared supportis treated with an alcohol and then the support is allowed to carrytitanium tetrachloride and an electron-donating compound(JP-A-63-280707) or a method in which a mixture of silicon tetrachloridewith silane trichloride is brought into contact with a product preparedby bringing silica and butyl octyl magnesium into contact, then, theresultant mixture is washed with an inert solvent to form amagnesium-chloride-supporting silica support, and the thus-preparedsupport is treated with an alcohol and then allowed to carry titaniumtetrachloride and an electron-donating compound (Japanese SpecificationPublication No. 4-506833 of PCT Application).

Further, there is also known a method in which silica, butyl ethylmagnesium and ethanol are brought into contact to form amagnesium-ethoxide-supporting silica support, the thus-formed support isreacted with silicon tetrachloride and then washed with heptane, and thethus-prepared support is further reacted with an electron-donatingcompound at 50° C. and with titanium tetrachloride at 90° C. once each(JP-A-61-174206), a method in which silica is impregnated with a mixtureof magnesium chloride with butanol to form a silica support supporting abutanol complex of magnesium chloride and the silica support is allowedto carry titanium tetrachloride and an electron-donating compound(JP-A-63-168413), or a method in which silica pre-treated with trimethylchlorosilane is allowed to carry diethoxymagnesium and then allowed tocarry titanium tetrachloride and an electron-donating compound(JP-B-7-17695).

However, while olefin polymers obtained by the above methods havecertain performances, particularly, the above methods or the olefinpolymers are not fully satisfactory in polymerization activity,stereoregularity, residual C1, and the like.

On the other hand, as a method of improving olefin polymers in themorphology including a particle diameter and a form, JP-A-58-000811discloses a method in which a magnesium compound is once dissolved in asolvent such as an alcohol and then re-precipitated and thethus-obtained precipitate is used.

In the above method, however, it is essential to carry out theprocedures of supporting, dissolving and precipitation of a magnesiumcompound, so that there are defects that steps thereof are complicatedand that a catalyst is poor in stability of performances. Further, theabove method also has another defect that the catalyst activity duringpolymerization and the stereoregularity of an olefin polymer are notsufficient.

As a method of overcoming the above defects, therefore, JP-A-2-02-413883discloses a method in which metal magnesium, an alcohol and a specificamount of a halogen reaction product are used as a support for acatalyst, and JP-B-07-025822 discloses a method of producing an olefinpolymer in the presence of a Ziegler-Natta catalyst containing a solidcatalyst component obtained by adding an organic acid ester to areaction product from alkoxymagnesium, a halogenating agent andalkoxytitanium and further reacting a titanium halide with the resultantmixture.

Further, there is known a method of producing an olefin polymer in thepresence of a solid catalyst component obtained by suspendingdiethoxymagnesium in alkylbenzene, reacting the diethoxymagnesium withpredetermined amounts of titanium tetrachloride and phthalic aciddiester at a temperature of 80° C. or higher but 120° C. or lower, toobtain a solid substance, washing the solid substance with alkylbenzeneand reacting the solid substance with a predetermined amount of titaniumtetrachloride in the presence of alkylbenzene (JP-A-64-69608).

In these methods, however, the catalytic activity during polymerizationand the stereoregularity of olefin polymers are not yet sufficient.

Further, JP-A-11-269218 discloses a solid catalyst component for olefinpolymerization, obtained by bringing a magnesium compound and a titaniumcompound into contact with each other in the presence of anelectron-donating compound at a temperature of 120° C. or higher but150° C. or lower and then washing the reaction mixture with an inertsolvent at a temperature of 100° C. or higher but 150° C. or lower.There are produced effects that a decrease in the catalytic activitywith the passage of time during polymerization is suppressed and that anolefin polymer is improved in stereoregularity.

Since, however, the polymerization activity of the above catalyst is notnecessarily fully satisfactory, the catalyst needs a further improvementin this activity.

It is an object of the present invention to provide a solid catalystcomponent for olefin polymerization, which has high polymerizationactivity and which gives an olefin polymer excellent instereoregularity, residual C1 and the state of a powder, a catalyst forolefin polymerization and a process for producing an olefin polymer.

For achieving the above object, the present inventors have made diligentstudies and as a result have found that a solid catalyst component forolefin polymerization, of which the residual alkoxy-group content isremarkably decreased, can be obtained by a specific production method,and that the above problems can be thereby overcome. The presentinvention has been accordingly completed.

DISCLOSURE OF THE INVENTION

[A1] Solid Catalyst Component for Olefin Polymerization

According to the present invention, there is provided a solid catalystcomponent for olefin polymerization, which is a reaction product fromthe following compounds (a1), (b1), (c1), (d1) and (e), and which isobtained by reacting the following compound (a1) with the followingcompound (b1) at a hydroxyl group/magnesium molar ratio of 1.0 or more,then, reacting the following compound (a1) with the following compound(c1) at a halogen/magnesium molar ratio of 0.20 or more, reacting areaction product from the following compounds (a1), (b1) and (c1) withthe following compound (d1) and the following compound (e) at atemperature of 120° C. or higher but 150° C. or lower, washing theresultant reaction mixture with an inert solvent, then, reacting thefollowing compound (e) again at a temperature of 120° C. or higher but150° C. or lower and washing the resultant reaction mixture with aninert solvent,

(a1) an oxide of at least one element that is selected from Group II toGroup IV elements and which supports an alcohol-free halogen-containingmagnesium compound,

(b1) an alcohol,

(c1) a halogen-containing silicon compound,

(d1) an electron-donating compound, and

(e) a halogen-containing titanium compound.

When prepared in the above manner, there can be obtained a solidcatalyst component that has high polymerization activity and which cangive an olefin polymer having a less residual C1 content and havingexcellence in stereoregularity and a powder form.

Particularly, when the hydroxyl group/magnesium molar ratio is adjustedto 1.0 or more, the crystallizability of a halogen-containing magnesiumcompound supported on an oxide of at least one of Group II to Group IVelements can be decreased, and there can be produced a support forsupporting an effective active species.

Further, when the halogen/magnesium molar ratio is adjusted to 0.20 ormore, an alcohol component that forms a complex, or reacts, with ahalogen-containing magnesium compound supported on an oxide of at leastone of the Group II to Group II elements can be efficiently extractedfrom the solid surface.

Presumably, the above preparation method promotes a reaction of analcohol or an alkoxy group contained in a reaction product from thecompounds (a1) and (b1) with the compounds (c1) and (e), so that thealkoxy group imparted directly to the magnesium compound is decreased,and alkoxytitanium, etc., produced as by-products come to be easilyextracted from the solid surface.

The above “again” means once or more. That is, after the compounds (a1)to (e) are allowed to react, the resultant reaction mixture and thecompound (e) may be further reacted at least once (e.g., once, twice ormore).

Further, the temperature for washing the reaction mixture obtained afterthe first reaction of the compounds (a1) to (e) with an inert solvent ispreferably at 100° C. or higher, but 150° C. or lower.

Further, the molar ratio (RO/Ti) of residual alkoxy groups (RO) to thesupported titanium (Ti) is preferably 0.60 or less.

According to another aspect of the present invention, there is provideda solid catalyst component for olefin polymerization, which is areaction product from the following compounds (a1), (b1), (c1), (d1) and(e) and in which the molar ratio (RO/Ti) of residual alkoxy groups (RO)to supported titanium (Ti) is 0.60 or less,

(a1) an oxide of at least one element that is selected from Group II toGroup IV elements and which supports an alcohol-free halogen-containingmagnesium compound,

(b1) an alcohol,

(c1) a halogen-containing silicon compound,

(d1) an electron-donating compound, and

(e) a halogen-containing titanium compound.

When the molar ratio (RO/Ti) is adjusted to 0.60 or less, there can beobtained a solid catalyst component that has high polymerizationactivity and which can give an olefin polymer having a less residual C1content and having excellence in stereoregularity and a powder form.

Further, the alcohol (b1) is preferably ethanol.

Further, the halogen-containing silicon compound (c1) is preferablysilicon tetrachloride.

The rate and reaction ratio of halogenation and dealkoxylation of areaction product, which is from the compound (a1) and the compound (b1),with silicon tetrachloride can be fully controlled presumably due to theuse of silicon tetrachloride.

Further, the molar ratio (RO/Ti) is preferably 0.45 or less.

The content of the residual alkoxy group (RO) is preferably 0.40 mmol/gor less.

The amount of the supported titanium is preferably 1.0% by weight ormore.

[A2] Solid Catalyst Component for Olefin Polymerization

According to the present invention, there is provided a solid catalystcomponent for olefin polymerization, which is a reaction productobtained by reacting the following compounds (a2) and (b2-1), reactingthe reaction mixture with the following compounds (c2) and (d2) at atemperature of 120° C. or higher but 150° C. or lower, washing thereaction product with an inert solvent, then, reacting the followingcompound (d2) again at a temperature of 120° C. or higher but 150° C. orlower and washing the reaction product with an inert solvent,

(a2) an oxide of at least one element selected from the Group II toGroup IV elements, the oxide supporting an alkoxy-group-containingmagnesium compound or an alcohol complex of a halogen-containingmagnesium compound,

(b2-1) a halogen-containing silicon compound whose amount as ahalogen/magnesium molar ratio is at least 0.20 based on the oxide (a2),

(c2) an electron-donating compound, and

(d2) a halogen-containing titanium compound.

When a solid catalyst component is prepared in the above manner, thecontent of residual alkoxy groups can be decreased, the solid catalystcomponent has high polymerization activity, and there can be obtained anolefin polymer having a less residual C1 content and having excellencein stereoregularity and a powder form.

Particularly, when the amount, as a halogen/magnesium molar ratio, ofthe compound (b2-1) is adjusted to 0.20 or more, alkoxy groups or analcohol in the alkoxy-group-containing magnesium compound or the alcoholcomplex of the halogen-containing magnesium compound can be efficientlyextracted from the solid surface of the (a2) component.

When the above preparation method is employed, presumably, the reactionof the alkoxy groups or alcohol contained in the reaction product fromthe compound (a2) and the compound (b2-1) with the compound (d2) ispromoted, the content of the alkoxy groups bonded to and contained inthe magnesium compound or the alcohol forming a complex therewith isdecreased, and alkoxytitanium etc. formed as a by-product comes to beeasily extracted from the solid surface.

The above “again” means once or more. That is, after the compounds (a2)to (d2) are reacted, the resultant reaction product and the compound(d2) may be further reacted at least once (e.g., once, twice or more).

Further, preferably, the temperature for the washing with the inertsolvent after the first reaction of the compounds (a2) to (d2) is 100°C. or higher but 150° C. or lower.

The molar ratio (RO/Ti) of residual alkoxy groups (RO) to the supportedtitanium (Ti) is preferably 0.70 or less.

According to another aspect of the present invention, there is provideda solid catalyst component for olefin polymerization, which is areaction product obtained by reacting

(a2) an oxide of at least one element selected from the Group II toGroup IV elements, the oxide supporting an alkoxy-group-containingmagnesium compound or an alcohol complex of a halogen-containingmagnesium compound,

(b2) a halogen-containing silicon compound,

(c2) an electron-donating compound, and

(d2) a halogen-containing titanium compound, and in which the molarratio (RO/Ti) of residual alkoxy groups (RO) to supported titanium (Ti)is 0.70 or less.

When the molar ratio (RO/Ti) is adjusted to 0.70 or less, there can beobtained a solid catalyst component that has high polymerizationactivity and which can give an olefin polymer having a less residual C1content and having excellence in stereoregularity and a powder form.

Further, each of the halogen-containing silicon compounds (b2) and(b2-1) is preferably silicon tetrachloride.

The rate and reaction ratio of halogenation and dealkoxylation reactionof the (a2) component with silicon tetrachloride can be fully controlledpresumably due to the use of silicon tetrachloride.

Further, the molar ratio (RO/Ti) is preferably 0.50 or less.

The content of the residual alkoxy groups (RO) is preferably 0.5 mmol/gor less.

The amount of the supported titanium is preferably 1.0% by weight ormore.

[A3] Solid Catalyst Component for Olefin Polymerization

According to the present invention, there is provided a solid catalystcomponent for olefin polymerization, which is a reaction productobtained by reacting the following compounds (a3) to (c3-1) (that is,compound (a3), compound (b3) and compound (c3-1)) or the followingcompounds (a3) to (d3) (that is, compound (a3), compound (b3), compound(c3-1) and compound (d3)) at a temperature of 120° C. or higher but 150°C. or lower, washing the reaction mixture with an inert solvent, furtherreacting the reaction mixture with the following halogen-containingtitanium compound (a3) at least once (e.g., once, twice, or the like) ata temperature of 120° C. or higher but 150° C. or lower, and washing thereaction mixture with an inert solvent,

(a3) a halogen-containing titanium compound,

(b3) an alkoxy-group-containing magnesium compound,

(c3-1) a halogen-containing silicon compound in which the molar ratio ofhalogen to the alkoxy group of the alkoxy-group-containing magnesiumcompound (b3) is 0.50 or more,

(d3) an electron-donating compound.

When the solid catalyst component is prepared in the above manner, thecontent of residual alkoxy groups can be decreased, the solid catalystcomponent has high polymerization activity, and an olefin polymerexcellent in the form of a powder can be obtained.

According to another aspect of the present invention, there is provideda solid catalyst component for olefin polymerization, which is obtainedby reacting the following compounds (a3) to (c3) (that is, compound(a3), compound (b3) and compound (c3)) or the following compounds (a3)to (d3) (that is, compound (a3), compound (b3), compound (c3) andcompound (d3)) and in which the molar ratio (RO/Ti) of residual alkoxygroups (RO) to supported titanium (Ti) is 0.30 or less,

(a3) a halogen-containing titanium compound,

(b3) an alkoxy-group-containing magnesium compound,

(c3) a halogen-containing silicon compound,

(d3) an electron-donating compound.

When the molar ratio (RO/Ti) is adjusted to 0.30 or less, the solidcatalyst component has high polymerization activity, and an olefinpolymer excellent in the form of a powder can be obtained.

In the compound (c3), preferably, the molar ratio of the halogen of thecompound (c3) to the alkoxy group of the compound (b3) is 0.50 or more.

When the molar ratio is adjusted to 0.50 or more, presumably, thehalogenation of the compound (b3) with the compound (c3) effectivelyproceeds, so that the halogenation degree of the compound (b3) isfinally improved and that the formation of an alkoxytitanium compoundexpectably formed as a byproduct is inhibited, whereby the solidcatalyst component is improved in polymerization activity.

In some cases, presumably, the halogenation of the compound (b3) withthe compound (c3) proceeds in preference to the halogenation of thecompound (b3) with the compound (a3), so that the halogenation rate ofthe compound (b3) is decreased, and that the formation of a finercatalyst, and the like are inhibited, whereby the solid catalystcomponent is excellent in a powder form.

By the above preparation method, presumably, the halogenation of thecompound (b) with the compounds (a3) and (c3) is promoted, and analkoxytitanium compound, etc., which are assumed to be formed as abyproduct, come to be easily extracted from a solid surface.

Further, the compound (b3) is preferably a compound obtained by reactingmetal magnesium, an alcohol and a halogen and/or a halogen-containingcompound containing at least 0.0001 gram atom, per mole of the metalmagnesium, of halogen atoms.

When the amount of the halogen and/or halogen-containing compound issmaller than the above amount, the compound (b3) may come to have largeand broad particle diameters, and the halogenation degree of thecompound (b3) may be suppressed, and the extraction efficiency ofalkoxytitanium, etc., may be decreased.

The use of the above compound (b3) can improve an olefin polymer inmorphology. The above-prepared compound (b3) is nearly spherical andrequires no classification procedures.

In the preparation of the solid catalyst component of the presentinvention, the electron-donating compound (d3) is used as required. Thesolid catalyst component obtained without the electron-donating compound(d3) is particularly suitable as a catalyst for the production of anethylene homopolymer or an ethylene copolymer and has highpolymerization activity.

[A4] Solid Catalyst Component for Olefin Polymerization

According to the present invention, there is provided a solid catalystcomponent for olefin polymerization, which is a reaction productobtained by reacting the following compounds (a4) and (b4) or thefollowing compounds (a4), (b4) and (c4) in the presence of an aromatichydrocarbon solvent at a temperature of 120° C. or higher but 150° C. orlower, washing the reaction mixture with an inert solvent, furtherreacting the following halogen-containing titanium compound (a4) atleast once (e.g., once, twice, etc.) at a temperature of 120° C. orhigher but 150° C. or lower and washing the reaction mixture with aninert solvent,

(a4) a halogen-containing titanium compound,

(b4) an alkoxy-group-containing magnesium compound,

(c4) an electron-donating compound.

When the solid catalyst component is prepared in the above manner, thecontent of residual alkoxy groups in the solid catalyst component can bedecreased, the solid catalyst component has high polymerizationactivity, and an olefin polymer excellent in a powder form can beobtained.

According to another aspect of the present invention, there is provideda solid catalyst component for olefin polymerization, which is areaction product obtained by reacting the following compounds (a4) and(b4) or the following compounds (a4), (b4) and (c4) in the presence ofan aromatic hydrocarbon solvent and in which the molar ratio (RO/Ti) ofresidual alkoxy groups (RO) to supported titanium (Ti) is 0.25 or less,

(a4) a halogen-containing titanium compound,

(b4) an alkoxy-group-containing magnesium compound,

(c4) an electron-donating compound.

When the molar ratio (RO/Ti) is adjusted to 0.25 or less, there can beprepared a solid catalyst component having high polymerization activityand being capable of giving an olefin polymer excellent in a powderform.

In the preparation of the solid catalyst component of the presentinvention, the electron-donating compound (c4) is used as required. Thesolid catalyst component obtained without the electron-donating compound(c4) is particularly suitable as a catalyst for the production of anethylene homopolymer or an ethylene copolymer and has highpolymerization activity.

Further, preferably, the compound (b4) is an alkoxy-group-containingmagnesium compound obtained by reacting metal magnesium, an alcohol anda halogen and/or halogen-containing compound containing at least 0.0001gram atom, per mole of the above metal magnesium, of halogen atoms.

In this case, when the amount of the halogen and/or halogen-containingcompound for use in the preparation of the compound (b4) is smaller thanthe above amount, the compound (b4) may come to have large and broadparticle diameters, and the halogenation degree of the compound (b4)with the compound (a4) may be decreased, and the efficiency ofextraction of alkoxytitanium adsorbed on the compound (b4) may bedecreased.

The use of the above alkoxy-group-containing magnesium compound (b4) canimprove an olefin polymer in morphology. The above-preparedalkoxy-group-containing magnesium compound (b4) is nearly spherical andrequires no classification procedures.

By the above preparation method, presumably, the halogenation of thecompound (b4) with the compound (a4) is promoted, and an alkoxytitaniumcompound, etc., which are assumed to be formed as a byproduct, come tobe easily extracted from the surface of a solid that constitutes thesolid catalyst component.

[Catalyst for Olefin Polymerization]

According to still another aspect of the present invention, there isprovided a catalyst for olefin polymerization, containing the followingcomponents [A] and [B] or the following components [A], [B] and [C].

[A] any one of the above solid catalyst components [A1] to [A4] forolefin polymerization,

[B] an organic aluminum compound,

[C] an electron-donating compound.

The electron-donating compound [C] is incorporated as required. Whenthis compound is incorporated, an olefin polymer can be sometimesimproved in stereoregularity and/or the catalyst can be sometimesimproved in polymerization activity.

[Process for Producing Olefin Polymer]

According to further another aspect of the present invention, there isprovided a process for producing an olefin polymer, which comprisespolymerizing an olefin in the presence of the above catalyst for olefinpolymerization.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic drawing for showing the catalyst for olefinpolymerization, provided by the present invention, and a process forproducing an olefin polymer.

FIG. 2 is a schematic drawing for showing another catalyst for olefinpolymerization, provided by the present invention, and a process forproducing an olefin polymer.

FIG. 3 is a schematic drawing for showing still another catalyst forolefin polymerization, provided by the present invention, and a processfor producing an olefin polymer.

FIG. 4 is a schematic drawing for showing yet another catalyst forolefin polymerization, provided by the present invention, and a processfor producing an olefin polymer.

PREFERRED EMBODIMENTS OF THE INVENTION

The catalyst components, preparation methods thereof, the polymerizationprocess, and the like in the present invention will be explainedhereinafter. Embodiments shown hereinafter are preferred embodiments,and the present invention shall not be limited by them so long as itsatisfies the requirements of claims.

1. Catalyst Components

[A1] Solid Catalyst Component for Olefin Polymer

(a1) The oxide of at least one element that is selected from Group II toGroup IV elements and which supports an alcohol-free halogen-containingmagnesium compound.

The oxides of Group II to Group IV elements include solid oxidescontaining at least one of these elements each and solid compositeinorganic oxides thereof. As Group II to Group IV elements, Mg, Ca, B,Al, Si and Sn are preferred, Al and Si are more preferred, and Si isparticularly preferred.

The solid oxide includes, for example, MgO, CaO, B₂O₃, SiO₂, SnO₂ andAl₂O₃.

Further, the solid composite inorganic oxide include, for example,SiO₂—Al₂O₃, SiO₂—MgO, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—Cr2O₃ andSiO₂—TiO₂—MgO.

These various solid oxides and solid composite inorganic oxides may beused alone, or two or more solid oxides or solid composite inorganicoxides of these may be simultaneously used in combination. Further,solid oxide(s) and solid composite inorganic oxide(s) of these may besimultaneously used in combination.

The above solid oxide component constitutes a basic element of acatalyst support. Therefore, when the solid oxide component is definedfrom the viewpoint of properties of a support, desirably, it has anaverage particle diameter D50 of 0.1 to 1,000 μm, particularlydesirably, 5 to 100 μm, a specific surface area of 10 to 1,000 m²/g,particularly desirably, 100 to 800 m²/g and a pore volume of 0.1 to 5cm³/g, particularly desirably, 1 to 2.5 cm³/g. The above averageparticle diameter (D50) is defined to be a particle diametercorresponding to 50% of a cumulative weight percentage. That is, itshows that the total sum of weight of particles smaller than a particlediameter expressed by D50 is 50% of the total sum of weight of theentire particles.

Of the solid oxide components, SiO₂ that can have the above propertiesis particularly preferred.

The alcohol-free halogen-containing magnesium compound includesmagnesium dihalides such as magnesium chloride, magnesium bromide andmagnesium iodide, alkoxymagnesium halides such as butoxymagnesiumchloride, cyclohexyloxymagnesium chloride, phenoxymagnesium chloride,ethoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesiumbromide and ethoxymagnesium iodide, allyloxymagnesium halide,alkylmagnesium halides such as butylmagnesium chloride,cyclohexylmagnesium chloride, phenylmagnesium chloride, ethylmagnesiumchloride, ethylmagnesium bromide, butylmagnesium bromide andethylmagnesium iodide and allylmagnesium halide. Of thesehalogen-containing magnesium compounds, magnesium chloride isparticularly preferred in view of catalyst performances.

The alcohol-free halogen-containing magnesium compound is not speciallylimited in composition. Desirably, in view of activity etc., themagnesium/oxide (a1) weight ratio is generally 0.1 to 20 wt %,preferably 1 to 15 wt %, particularly preferably 4 to 12 wt %.

The method of allowing the above oxide to support the alcohol-freehalogen-containing magnesium compound can be selected from a method inwhich the solid oxide and magnesium dihalide, alkoxymagnesium halide,allyloxymagnesium halide, alkylmagnesium halide or allymagnesium halideare directly brought into contact with each other, or a method in whichthe solid oxide and dialkylmagnesium or dialkoxymagnesium are oncebrought into contact with each other and then a halogenation agent suchas hydrogen chloride is brought into contact with them, to partially orcompletely halogenate the dialkylmagnesium or dialkoxymagnesium, and soon.

(b1) Alcohol

The alcohol is preferably selected from lower alcohols having 1 to 8carbon atoms. It is particularly preferred to use ethanol, since a solidproduct that remarkably improves a catalyst in performances can beobtained. While the purity and water content of the alcohol are notcritical, a catalyst is degraded in performances such as activity whenan alcohol having a large water content is used. It is thereforepreferred to use an alcohol having a water content of 1% or less,particularly preferably, 2,000 ppm or less. Further, for attainingbetter catalyst performances, the smaller the water content, the morepreferred it is, and the water content is desirably 200 ppm or less.

(c1) Halogen-containing silicon compound

The halogen-containing silicon compound can be selected from compoundsrepresented by the following general formula (I).Si(OR¹)_(r)X¹ _(4-r)   (I)

When the halogen-containing silicon compound (c1) is used, the catalystactivity during polymerization can be sometimes improved, a polymer canbe sometimes improved in stereoregularity, and the content of a fineparticle in a polymer can be sometimes decreased.

In the above general formula (I), X¹ is a halogen atom, and the halogenatom is preferably a chlorine or bromine atom, particularly preferably achlorine atom. R¹ is a hydrocarbon group, and may be a saturated groupor an unsaturated group. It may be linear or branched, or it may becyclic, and it may contain a hetero atom such as sulfur, nitrogen,oxygen, silicon or phosphorus. Of these, R¹ is preferably a hydrocarbongroup having 1 to 10 carbon atoms, particularly preferably an alkylgroup, an alkenyl group, a cycloalkenyl group, an aryl group or anaralkyl group. When a plurality of groups as OR¹ are present, one ofthese may be the same as, or different from, the other or every otherone. Specific examples of R¹ include methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-decyl, allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl,tolyl, benzyl and phenethyl. And, r is an integer of 0 to 3.

Specific examples of the halogen-containing silicon compounds of theabove general formula (I) include silicon tetrachloride,methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane,ethoxytrichlorosilane, diethoxydichlorosilane, triethoxychlorosilane,propoxytrichlorosilane, dipropoxydichlorosilane andtripropoxychlorosilane. Of these, silicon tetrachloride is particularlypreferred. The above halogen-containing silicon compounds may be usedsolely, or two or more compounds of them may be used in combination.

(d1) Electron-donating compound

The electron-donating compound includes oxygen-containing compounds suchas alcohols, phenols, ketones, aldehydes, carboxylic acids, malonicacid, esters of organic acids or inorganic acids and ethers such asmonoether, diether and polyether, and nitrogen-containing compounds suchas ammonia, amine, nitrile and isocyanate. Of these, esters ofpolyhydric carboxylic acids are preferred, and esters of aromaticpolyhydric carboxylic acids are more preferred. Of these, a monoesterand/or a diester of aromatic dicarboxylic acid are/is particularlypreferred in view of catalyst activity during polymerization. Further,the organic group of an ester portion is preferably a linear, branchedor cyclic aliphatic hydrocarbon group.

Specific examples of the electron-donating compound include dialkylesters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-hexyl, cyclohexyl,n-heptyl, n-octyl, n-nonyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl,2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl,3-methylpentyl, 2-ethylpentyl or 3-ethylpentyl dicarboxylates such asphthalate, naphthalene-1,2-dicarboxylate, naphthalene-2,3-dicarboxylate,5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylate,5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylate, indan-4,5-dicarboxylateand indan-5,6-dicarboxylate. Of these, phthalic acid diesters arepreferred, and phthalic acid diesters in which the organic group of anester portion is a linear or branched aliphatic hydrocarbon group having4 or more carbon atoms are particularly preferred. Specific examples ofthese include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptylphthalate and diethyl phthalate. These compounds may be used solely, ortwo or more compounds of them may be used in combination.

(e) Halogen-containing titanium compound

The halogen-containing titanium compound can be preferably selected fromcompounds represented by the following general formula (II).TiX² _(p)(OR²)_(4-p)   (II)

In the above general formula (II), X² is a halogen atom, and the halogenatom is preferably a chlorine or bromine atom, particularly preferably achlorine atom. R² is a hydrocarbon group, and may be a saturated groupor an unsaturated group. It may be linear or branched, or it may becyclic, and it may contain a hetero atom such as sulfur, nitrogen,oxygen, silicon or phosphorus. Of these, R² is preferably a hydrocarbongroup having 1 to 10 carbon atoms, particularly preferably an alkylgroup, an alkenyl group, a cycloalkenyl group, an aryl group or anaralkyl group. R² is particularly preferably a linear or branched alkylgroup. When a plurality of groups as OR² are present, one of these maybe the same as, or different from, the other or every other one.Specific examples of R² include methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-decyl, allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl,tolyl, benzyl and phenethyl. And, p is an integer of 1 to 4.

Specific examples of the halogen-containing titanium compounds of theabove general formula (II) include titanium tetrahalides such astitanium tetrachloride, titanium tetrabromide and titanium tetraiodide;alkoxytitanium trihalides such as methoxytitanium trichloride,ethoxytitanium trichloride, propoxytitanium trichloride,n-butoxytitanium trichloride and ethoxytitanium tribromide;dialkoxytitanium dihalides such as dimethoxytitanium dichloride,diethoxytitanium dichloride, diisopropoxytitanium dichloride,di-n-propoxytitanium dichloride and diethoxytitanium dibromide; andtrialkoxytitanium monohalides such as trimethoxytitanium chloride,triethqxytitanium chloride, triisopropoxytitanium chloride,tri-n-propoxytitanium chloride and tri-n-butoxytitanium chloride. Ofthese, high-halogenated titanium compounds are preferred, and titaniumtetrachloride is particularly preferred, in view of polymerizationactivity. These halogen-containing titanium compounds may be usedsolely, or two or more compounds of these may be used in combination.

[A2] Solid Catalyst Component for Olefin Polymerization

(a2) Oxide of at least one element selected from the Group II to GroupIV elements, the oxide supporting an alkoxy-group-containing magnesiumcompound or an alcohol complex of a halogen-containing magnesiumcompound.

The oxide of at least one element selected from the Group II to Group IVelements and the halogen-containing magnesium compound are as explainedwith regard to the above oxide (a1), so that their explanations areomitted.

The alkoxy-group-containing magnesium compound includesdialkoxymagnesium compounds such as dimethoxymagnesium,diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium,dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium anddicyclohexyloxymagnesium, diallyloxymagnesium; alkoxyalkylmagnesiumcompounds such as ethoxyethylmagnesium, phenoxymethylmagnesium,ethoxyphenylmagnesium, cyclohexyloxyphenylmagnesium,allyloxyalkylmagnesiu, alkoxyallylmagnesium, allyloxyallylmagnesium;alkoxymagnesium halides such as butoxymagnesium chloride,cyclohexyloxymagnesium chloride, phenoxymagnesium chloride,ethoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesiumbromide and ethoxymagnesium iodide, and allyloxymagnesium halides. Ofthese alkoxy-group-containing magnesium compounds, dialkoxymagnesiumcompounds are preferred, and diethoxymagnesium is particularlypreferred, in view of catalyst performances.

The alcohol is preferably selected from lower alcohols having 1 to 8carbon atoms, such as methanol, ethanol, propanol, butanol, and thelike. Of these, ethanol is particularly preferred.

While the alkoxy-group-containing magnesium compound or the alcoholcomplex of the halogen-containing magnesium compound is not speciallylimited concerning its composition, the magnesium/oxide (a2) weightratio is generally 0.1 to 20 wt %, preferably 1 to 15 wt %, particularlypreferably 2 to 12 wt %, in view of activity, and the like.

The method of allowing the above oxide to support thealkoxy-group-containing magnesium compound can be selected from a methodin which the solid oxide and the dialkoxymagnesium, diallyloxymagnesium,alkoxyalkylmagnesium, allyloxyalkylmagnesium, alkoxymagnesium halide orallyloxymagnesium halide are directly brought into contact with eachother, or a method in which the solid oxide and the dialkylmagnesium areonce brought into contact with each other and then an alcohol is broughtinto contact to partially or completely alkoxylate the dialkylmagnesium.

The method of allowing the above oxide to support the alcohol complex ofthe halogen-containing magnesium compound can be selected from a methodin which the solid oxide and the alcohol complex of the magnesiumdihalide, the alcohol complex of the alkoxymagnesium halide or thealcohol complex of the allyloxymagnesium halide are directly broughtinto contact with each other or a method in which the solid oxide andthe magnesium dihalide, alkoxymagnesium halide or allyloxymagnesiumhalide are once brought into contact with each other and then thealcohol is brought into contact to form the corresponding alcoholcomplex.

(b2) Halogen-containing silicon compound

The halogen-containing silicon compound (b2) is as explained with regardto the halogen-containing silicon compound (c1) for use in the solidcatalyst component [A1], so that its explanation is omitted.

(c2) Electron-donating compound

The electron-donating compound (c2) is as explained with regard to theelectron-donating compound (d1) for use in the solid catalyst component[A1], so that its explanation is omitted.

(d2) Halogen-containing titanium compound

The halogen-containing titanium compound (d2) is as explained withregard to the halogen-containing titanium compound (e) for use in thesolid catalyst component [A1], so that its explanation is omitted.

[A3] Solid Catalyst Component for Olefin Polymerization

(a3) Halogen-containing titanium compound

The halogen-containing titanium compound (a3) is as explained withregard to the halogen-containing titanium compound (e) for use in thesolid catalyst component [A1], so that its explanation is omitted.

(b3) Alkoxy-group-containing magnesium compound

The alkoxy-group-containing magnesium compound can be preferablyselected from compounds represented by the following general formula(III).Mg(OR³)_(q)R⁴ _(2-q)   (III)

In the above general formula (III), R³ is a hydrocarbon group, and R⁴ isa hydrocarbon group or a halogen atom. Each of the hydrocarbon grouprepresented by R³ and the hydrocarbon group represented by R⁴ includesan alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an arylgroup and an aralkyl group, and these hydrocarbon groups may be the sameas, or different from, each other. The halogen atom represented by R⁴includes chlorine, bromine, iodine and fluorine. And, q is an integer of1 to 2.

Specific examples of the alkoxy-group-containing magnesium compounds ofthe above general formula (III) include dialkoxymagnesium compounds suchas dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium,dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium,diphenoxymagnesium, dicyclohexyloxymagnesium, diallyloxymagnesium;alkoxyalkylmagnesium compounds such as ethoxyethylmagnesium,phenoxymethylmagnesium ethoxyphenylmagnesium andcyclohexyloxyphenylmagnesium, allyloxyalkylmagnesium,alkoxyallylmagnesium, allyloxyallylmagnesium; alkoxymagnesium halidessuch as butoxymagnesium chloride, cyclohexyloxymagnesium chloride,phenoxymagnesium chloride, ethoxymagnesium chloride, ethoxymagnesiumbromide, butoxymagnesium bromide and ethoxymagnesium iodide, andallyloxymagnesium halide.

Of these, dialkoxymagnesium compounds are preferred, anddiethoxymagnesium is particularly preferred, in view of polymerizationactivity and stereoregularity.

In view of the polymerization activity of the catalyst and the powderform and stereoregularity of an olefin polymer, preferably, thealkoxy-group-containing magnesium compound (b3) is obtained by reactingmetal magnesium, an alcohol and a halogen or halogen-containing compoundcontaining 0.0001 gram atom, per mole of the metal magnesium, of ahalogen.

The above metal magnesium is not critical with regard to its form, andthe like. Therefore, a metal magnesium having any particle diameter, forexample, a metal magnesium having a granular, ribbon-shaped or powderyform, may be used. While the surface state of the metal magnesium is notcritical, either, a metal magnesium having a surface free of a coatingof magnesium hydroxide, or the like is preferred.

The alcohol is preferably selected from lower alcohols having 1 to 6carbon atoms. Ethanol is particularly preferred, since ethanol serves togive a solid product that remarkably improves the exhibition ofcatalytic performances. While the purity and water content of thealcohol are not critical, either. When an alcohol having a large watercontent is used, however, magnesium hydroxide is formed on the metalmagnesium surface, so that it is preferred to use an alcohol having awater content of 1% or less, and it is particularly preferred to use analcohol having a water content of 2,000 ppm or less. Further, forattaining better morphology, a smaller water content is preferred, andthe water content is generally desirably 200 ppm or less.

The halogen is selected from chlorine, bromine or iodine, and iodine isparticularly suitably used.

Further, the halogen atom of the halogen-containing compound ispreferably chlorine, bromine or iodine. The halogen-containing compoundis particularly preferably a halogen-containing metal compound.Specifically, the halogen-containing compound can be preferably selectedfrom MgCl₂, MgI₂, Mg(OEt)Cl, Mg(OEt)I, MgBr₂, CaCl₂, NaCl or KBr etc. Ofthese, MgCl₂ is particularly preferred. The state, form and particlesize of these compounds are not limited, and a compound being in anystate and having any form and any particle size can be used. Forexample, a solution of such a compound in an alcohol solvent (e.g.,ethanol) can be used.

The amount of the alcohol per mole of the metal magnesium is preferably2 to 100 mol, particularly preferably 5 to 50 mol. When the amount ofthe alcohol is too large, the yield of the alkoxy-group-containingmagnesium compound (b3) having excellent morphology may decrease in somecases. When it is too small, stirring in a reaction vessel may notsmoothly proceed in some cases, while it is not limited by the molarratio.

The amount of the halogen as a halogen atom per mole of the metalmagnesium is 0.0001 gram atom or more, preferably 0.0005 gram atom ormore, more preferably 0.001 gram atom or more. When the amount of thehalogen is less than 0.0001 gram atom, there is no difference from acase where no halogen is used as a reaction initiator, and when thethus-obtained alkoxy-group-containing magnesium compound (b3) is used asa catalyst support, the catalyst may be poor in catalyst activity or anolefin polymer may be defective in morphology, and the like.

The amount of the halogen-containing compound, as a halogen atom in thehalogen-containing compound per mole of the metal magnesium, is at least0.0001 gram atom or more, preferably 0.0005 gram atom or more, morepreferably 0.001 gram atom or more. When the above amount is less than0.0001 gram atom, there is no difference from a case where nohalogen-containing compound is used as a reaction initiator, and whenthe thus-obtained alkoxy-group-containing magnesium compound (b3) isused as a catalyst support, the catalyst may be poor in catalystactivity, or an olefin polymer may be defective in morphology, and thelike.

In the present invention, the halogens or the halogen-containingcompounds may be used solely each, and two or more halogens orhalogen-containing compounds of these may be used in combination.Further, the halogen and the halogen-containing compound may be used incombination. When the halogen and the halogen-containing compound areused in combination, the amount of total halogen atoms in the halogenand the halogen-containing compound per mole of the metal magnesium is0.0001 gram atom or more, preferably 0.0005 gram atom or more, morepreferably 0.001 gram atom or more.

While the upper limit of the amount(s) of the halogen and/or thehalogen-containing compound is not specially limited, the upper limitmay be set as required so long as the alkoxy-group-containing magnesiumcompound (b3) for use in the present invention can be obtained.Generally, the above upper limit is preferably less than 0.06 gram atom.

In the process for the production of an olefin polymer, provided by thepresent invention, the amount of the halogen and/or thehalogen-containing compound is determined as required, whereby theparticle diameter of the alkoxy-group-containing magnesium compound (b3)can be controlled as required.

The preparation of the alkoxy-group-containing magnesium compound (b3)is carried out until the generation of hydrogen gas is no longerobserved (generally, for 1 to 30 hours). Specifically, when iodine isused as a halogen, the alkoxy-group-containing magnesium compound (b3)can be prepared by a method in which iodine in the form of a solid ischarged into the metal magnesium and the alcohol and then the mixture isallowed to react under heat, a method in which a solution of iodine inan alcohol is dropwise added to the metal magnesium and the alcohol andthe mixture is allowed to react under heat, or a method in which, whilethe metal magnesium and an alcohol solution are heated, a solution ofiodine in an alcohol is dropwise added to allow the mixture to react.

Each method is preferably carried out in the atmosphere of an inert gas(e.g., nitrogen gas or argon gas) and optionally in the presence of aninert organic solvent (e.g., saturated hydrocarbon such as n-hexane)

Further, it is not required to charge the entire amount of each of themetal magnesium, the alcohol and the halogen at once from the beginning,and they may be divided and partially charged. In a particularlypreferred embodiment, the alcohol is entirely charged in the beginning,the metal magnesium is divided into several portions and such portionsare charged separately. In this embodiment, the generation of a largeamount of hydrogen gas can be prevented, which is desirable in view ofsafety. Further, the size of a reaction vessel can be decreased.Further, it is also made possible to prevent the dissipation of alcoholand halogen caused by the momentary generation of a large amount ofhydrogen gas. While the number of the divisional portions can bedetermined by taking account of the size of the reaction vessel and isnot specially limited, suitably, each is generally divided into five toten portions in view of complicatedness of procedures.

Further, the reaction may be carried out by any one of a batch methodand a continuous method. Further, there may be employed a variant methodin which the entire amount of the alcohol is charged in the beginning, asmall amount of the metal magnesium is added to the alcohol, a productformed by a reaction is removed by separating it into other vessel,then, a small amount of the metal magnesium is charged, and theseprocedures are repeated.

Further, in view of the catalyst activity during polymerization and thepowder form of an olefin polymer, the metal magnesium, the alcohol andthe halogen and/or the halogen-containing compound are allowed to reactat 30 to 60° C., more preferably at 40 to 55° C., thereby to adjust theaverage particle diameter (D50) of the thus-obtainedalkoxy-group-containing magnesium compound (b3) to 50 μm or less, morepreferably 40 μm or less. The average particle diameter (D50) ispreferably 1 μm or more.

The average particle diameter (D50) is defined to be a particle diametercorresponding to 50% of a cumulative weight percentage. That is, itshows that the total sum of weight of particles having a smallerdiameter than the particle diameter expressed by D50 is 50% of the totalweight of the entire particles.

When the reaction temperature is adjusted to 30 to 60° C., the compound(b3) decreases in particle diameter while retaining the properties thatit is spherical and has a narrow particle size distribution, thehalogenation of the compound (b3) proceeds, and the amount of a residualalkoxy group content in the solid catalyst component can be decreased.When the reaction temperature is higher than the above temperaturerange, the decrease in particle diameter does not efficiently proceed.When it is lower than the above temperature range, the rate of formationof the compound (b3) greatly decreases, which results in a decrease inproductivity.

When the average particle diameter (DSO) is decreased to a smallerdiameter of as small as 50 μm or less, presumably, the compound (b3) isimproved in halogenation degree, and an alkoxytitanium compound and thelike, which are predictably formed as a byproduct, come to be easilyextracted from the solid surface.

When the alkoxy-group-containing magnesium compound (b3) is used for thepreparation of the solid catalyst component [A3], a dry product may beused, or a product obtained by washing a filtered product with heptane,or the like, may be used. In any case, the alkoxy-group-containingmagnesium compound (b3) can be used in a step to follow, without anypulverization or any sieving procedure for attaining a uniform particlediameter distribution. Further, the alkoxy-group-containing magnesiumcompound (b3) is nearly spherical and has a sharp particle diameterdistribution. Furthermore, the alkoxy-group-containing magnesiumcompound (b3) as individual particles has a small variability ofsphericity.

These alkoxy-group-containing magnesium compounds (b3) may be usedsolely, or two or more of them may be used in combination. Further, thealkoxy-group-containing magnesium compound (b3) may be used in a statewhere it is supported on a support such as silica, alumina orpolystyrene, or it may be used in the form of a mixture with a halogenand the like.

(c3) Halogen-containing silicon compound

The halogen-containing silicon compound (c3) is similar to thehalogen-containing silicon compound (c1) for use in the solid catalystcomponent [A1], so that a duplicate explanation will be omitted.

The halogen-containing silicon compound (c3) is particularly preferablysilicon tetrachloride.

Presumably, the use of silicon tetrachloride can fully control thereaction rate of the halogenation, and the conversion, of the compound(b3) with silicon tetrachloride.

Further, the compound (c3) is preferably a halogen-containing siliconcompound (c3-1) in which the molar ratio of a halogen to the alkoxygroup of the compound (b3) is 0.50 or more. When such ahalogen-containing silicon compound is used, the halogenation of thecompound (b3) proceeds, and the amount of residual alkoxy groups in thesolid catalyst component can be decreased. More preferably, the compound(c3) is a halogen-containing silicon compound in which the molar ratioof a halogen to the alkoxy group of the compound (b3) is 0.80 or more.

(d3) Electron-donating compound

The electron-donating compound (d3) for optional use in the preparationof the solid catalyst component [A3] is as explained with regard to theelectron-donating compound (d1) for use in the solid catalyst component[A1], so that its explanation is omitted.

[A4] Solid Catalyst Component for Olefin Polymerization

(a4) Halogen-containing titanium compound

The halogen-containing titanium compound (a4) is as explained withregard to the halogen-containing titanium compound (e) for use in thesolid catalyst component [A1], so that its explanation is omitted.

(b4) Alkoxy-group-containing magnesium compound

The alkoxy-group-containing magnesium compound (b4) is as explained withregard to the alkoxy-group-containing magnesium compound (b3) for use inthe solid catalyst component [A3], so that its explanation is omitted.

(c4) Electron-donating compound

The electron-donating compound (c4) for optional use in the preparationof the solid catalyst component [A4] is as explained with regard to theelectron-donating compound (d1) for use in the solid catalyst component[A1], so that its explanation is omitted.

[B] Organic Aluminum Compound

Although not specially limited, the organic aluminum compound [B] can bepreferably selected from an organic aluminum compound having an alkylgroup, a halogen atom, a hydrogen atom and an alkoxy group, aluminoxane,or a mixture of these. Specific examples thereof includetrialkylaluminum compounds such as trimethylaluminum, triethylaluminum,triisopropylaluminum, triisobutylaluminum and trioctylaluminum;dialkylaluminum monochlorides such as diethylaluminum monochloride,diisopropylaluminum monochloride, diisobutylaluminum monochloride anddioctylaluminum monochloride; alkylaluminum sesquihalides such asethylaluminum sesquichloride; and linear aluminoxanes such asmethylaluminoxane. Of these organic aluminum compounds, trialkylaluminumhaving a lower alkyl group having 1 to 5 carbon atoms is preferred, andtrimethylaluminum, triethylaluminum, tripropylaluminum andtriisobutylaluminum are particularly preferred. These organic aluminumcompounds may be used solely, or two or more compounds of these may beused in combination.

[C] Electron-Donating Compound

In the present invention of the catalyst for olefin polymerization,provided by the present invention, the electron-donating compound [C] isused as required. The electron-donating compound [C] can be selectedfrom an organosilicon compound having an alkoxy group, anitrogen-containing compound, a phosphorus-containing compound or anoxygen-containing compound. Of these, it is particularly preferred touse an organosilicon compound having an alkoxy group.

Specific examples of the organosilicon compound having an alkoxy groupinclude trimethylmethoxysilane, trimethylethoxysilane,triethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane,dimethyldiethoxysilane, ethylisopropyldimethoxysilane,propylisopropyldimethoxysilane, diisopropyldimethoxysilane,diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane,di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane,t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane,t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane,t-butylisobutyldimethoxysilane, t-butyl(s-butyl)dimethoxysilane,t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane,t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane,t-butylnonyldimethoxysilane, t-butyldecyldimethoxysilane,t-butyl(3,3,3-trifluromethylpropyl)dimethoxysilane,cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane,cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane,dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane,cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane,cyclopentylpropyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane,dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane,bis(2-methylcyclopentyl)dimethoxysilane,bis(2,3-dimethylcyclopentyl)dimethoxysilane,α-naphthyl-1,1,2-trimethylpropyldimethoxysilane,n-tetradecanyl-1,1,2-trimethylpropyldimethoxysilane,1,1,2-trimethylpropylmethyldimethoxysilane,1,1,2-trimethylpropylethyldimethoxysilane,1,1,2-trimethylpropylisopropyldimethoxysilane,1,1,2-trimethylpropylcyclopentyldimethoxysilane,1,1,2-trimethylpropylcyclohexyldimethoxysilane,1,1,2-trimethylpropylmyristyldimethoxysilane, diphenyldimethoxysilane,diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,propyltrimethoxysilane, isopropyltrimethoxysilane,butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane,t-butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane,isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornenetrimethoxysilane, indenyl trimethoxysilane,2-methylcyclopentyl trimethoxysilane, ethyltriisopropoxysilane,methylcyclopentyl(t-butoxy)dimethoxysilane,isopropyl(t-butoxy)dimethoxysilane, t-butyl(t-butoxy)dimethoxysilane,(isobutoxy)dimethoxysilane, vinyltriethoxysialen, vinyltributoxysilane,chlorotriethoxysilane, γ-chloropropyltrimethoxysilane,γ-aminopropyltriethoxysilane, 1,1,2-trimethylpropyltrimethoxysilane,1,1,2-trimethylpropylisopropoxydimethoxysilane,1,1,2-trimethylpropyl(t-butoxy)dimethoxysilane, tetramethoxysilane,tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, ethylsilicate, butyl silicate, trimethylphenoxysilane,methyltriallyloxysilane, vinyltris(β-methoxyethoxy)silane,vinyltrisacetoxysilane and dimethyltetraethoxydisiloxane. Theseorganosilicon compounds may be used solely, or two or more compounds ofthese may be used in combination.

Further, the above organosilicon compound also includes a compoundobtained by reacting a silicon compound having no Si—O—C bond with anorganic compound having an O—C bond in advance or by reacting thesecompounds during the polymerization of an α-olefin. Specifically, acompound obtained by reacting silicon tetrachloride and an alcohol isincluded.

Specific examples of the nitrogen-containing compound include2,6-substituted piperidines such as 2,6-diisopropylpiperidine,2,6-diisopropyl-4-methylpiperidine andN-methyl-2,2,6,6-tetramethylpiperidine; 2,5-substituted azolidines suchas 2,5-diisopropylazolidine and N-methyl-2,2,5,5-tetramethylazolidine;substituted methylenediamines such asN,N,N′,N′-tetramethylmethylenediamine andN,N,N′,N′-tetraethylmethylenediamine; and substituted imidazolidinessuch as 1,3-dibenzylimidazolidine and1,3-dibenzyl-2-phenylimidazolidine.

Specific examples of the phosphorus-containing compound includephosphorous acid esters such as triethyl phosphite, tri-n-propylphosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutylphosphite, diethyl-n-butyl phosphite and diethylphenyl phosphite.

Specific examples of the oxygen-containing compound include2,5-substituted tetrahydrofurans such as2,2,5,5-tetramethyltetrahydrofuran and2,2,5,5-tetraethyltetrahydrofuran; and dimethoxymethane derivatives suchas 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene,9,9-dimethoxyfluorene and diphenyldimethoxymethane.

2. Method of Preparation of Solid Catalyst Component

Method of preparing solid catalyst component [A1]

The method of preparing the solid catalyst component [A1] can be amethod in which the oxide (a1) of at least one element of Groups II toIV elements, the oxide (a1) supporting the above alcohol-freehalogen-containing magnesium compound, and a predetermined amount of thealcohol (b1) are brought into contact, and reacted, with each other,then, the reaction mixture is brought into contact, and reacted, with apredetermined amount of the halogen-containing silicon compound (c1),the reaction mixture is reacted with the electron-donating compound (d1)and the halogen-containing titanium compound (e) at a temperature of120° C. or higher but 150° C. or lower, and the reaction product iswashed with an inert solvent, and then is brought into contact, andallowed to react, with the halogen-containing titanium compound (e)again (at least once) at a temperature of 120° C. or higher but 150° C.or lower. The order of other contacts is not critical.

Preferably, the halogen-containing titanium compound (e) is brought intocontact with a reaction mixture obtained by bringing the compounds (a1)to (c1) into contact with one another, and then the electron-donatingcompound (d1) is brought into contact with the reaction mixture, sincethe solid catalyst component in this case can be sometimes improved inpolymerization activity.

Further, these components may be brought into contact in the presence ofan inert solvent such as a hydrocarbon, or each component may be dilutedwith an inert solvent such as a hydrocarbon before they are brought intocontact. Examples of the above inert solvent include aliphatic oralicyclic hydrocarbons such as octane, decane and ethylcyclohexane,aromatic hydrocarbons such as toluene, ethylbenzene and xylene,halogenated hydrocarbons such as chlorobenzene, tetrachloroethane andchlorofluorocarbon, and mixtures of these. Of these, an aliphatichydrocarbon and aromatic hydrocarbon are preferred, and an aliphatichydrocarbon is particularly preferred.

The amount of the above halogen-containing titanium compound (e) permole of magnesium of the above halogen-containing magnesium compound isgenerally 0.5 to 100 mol, preferably 1 to 50 mol. When the above molarratio is outside the above range, the catalyst activity is sometimesinsufficient.

Further, the amount of the electron-donating compound (d1) per mole ofthe above halogen-containing magnesium compound is generally 0.01 to 10mol, preferably 0.05 to 1.0 mol. When the above molar ratio is outsidethe above range, the catalyst activity is sometimes insufficient or anolefin polymer sometimes has insufficient stereoregularity.

The halogen-containing silicon compound (c1) is used in such an amountthat the molar ratio of the halogen to the magnesium of the abovehalogen-containing magnesium compound is 0.20 or more, preferably from0.4 to 4.0, more preferably from 1.0 to 2.5. When the above amount issmaller than the above range, the catalyst activity or the effect onimprovement in stereoregularity is not fully exhibited, and a formedpolymer is caused to have an increased amount of a fine powder and iscaused to have a decreased bulk density. When the above amount is toolarge, there is produced no further effect on these improvements.

The alcohol (b1) is used in such an amount that the molar ratio of thehydroxy group to the magnesium of the above halogen-containing magnesiumcompound is 1 or more, preferably from 2 to 5, more preferably from 2.5to 4. When the above amount is smaller than the above range, thecatalyst activity or the effect on improvement in stereoregularity isnot fully exhibited. When it is too large, there is not any furthereffect on these improvements.

After the above compounds (a1) to (e) are all added, they are broughtinto contact and allowed to react preferably in a temperature range of120 to 150° C., particularly preferably 125 to 140° C. When the abovecontact temperature is outside the above range, the catalyst activity orthe effect on improvement in stereoregularity is sometimes not fullyexhibited. Further, the above contact is carried out generally for 1minute to 24 hours, preferably 10 minutes to 6 hours. Differingdepending upon a type of a solvent when it is used and a contacttemperature, etc., the pressure for the contact is generally in therange of atmospheric pressure to 5 MPa, preferably atmospheric pressureto 1 MPa. During the contacting procedures, preferably, they are stirredin view of the uniformity and efficiency of the contact. These contactconditions are also applicable to the contact reaction that is carriedout for the second time or more with regard to the halogen-containingtitanium compound (e).

When a solvent is used in the contact procedure of thehalogen-containing titanium compound (e), the amount of the solvent permole of the halogen-containing titanium compound (e) is generally 5,000milliliters or less, preferably 10 to 1,000 milliliters. When the aboveratio is outside the above range, the uniformity or efficiency of thecontact may be sometimes degraded.

Further, it is sometimes desirable to wash a reaction product, which isfrom the first contact reaction of the halogen-containing titaniumcompound (e), with an inert solvent at a temperature of 100 to 150° C.,particularly preferably 120 to 140° C. When the above washingtemperature is outside the above range, the catalyst activity or theeffect on improvement in stereoregularity is sometimes not exhibited.The inert solvent can be selected from the already explained solvents.

With regard to the washing temperature after the contact reaction whichis carried out for the second time or more with the halogen-containingtitanium compound (e), the washing is preferably carried out with aninert solvent at a temperature of 100 to 150° C., particularlypreferably 120 to 140° C., in view of stereoregularity.

The washing method is preferably selected from a decantation orfiltering method. Although the amount of the inert solvent, the washingtime period and the number of times of the washing are not critical, thewashing is carried out generally with a solvent in an amount, per moleof the magnesium compound, of 100 to 100,000 milliliters, preferably 500to 50,000 milliliters, generally for 1 minute to 24 hours, preferably 10minutes to 6 hours. When the above ratio is outside the above range, thewashing may be incomplete.

While the pressure in the above case differs depending upon the type ofthe solvent, the washing temperature, and the like, the pressure isgenerally in the range of atmospheric pressure to 5 MPa, preferablyatmospheric pressure to 1 MPa. For the uniformity of the washing and thewashing efficiency, it is preferred to stir the reaction mixture duringthe washing. The thus-obtained solid catalyst component can be stored ina dry state or in an inert solvent such as a hydrocarbon.

In the above-obtained solid catalyst component [A1], preferably, themolar ratio (RO/Ti) of the residual alkoxy group (RO) to the supportedtitanium (Ti) is 0.60 or less. That is because when the molar ratioexceeds 0.60, no intended catalyst may be obtained.

Further, the above molar ratio is more preferably 0.45 or less, stillmore preferably 0.35 or less.

Further, the residual alkoxy group content (RO) is preferably 0.40mmol/g or less. The reason therefore is that when the residual alkoxygroup content exceeds 0.40 mmol/g, the catalyst is poor in activity, thecatalyst cost increases and the amount of catalyst residues such as C1,etc., in a powder increases, so that a product quality may be sometimesdegraded.

Further, the residual alkoxy group content is more preferably 0.25mmol/g, still more preferably 0.15 mmol/g.

When the catalyst is prepared under the specific reaction conditions,the residual alkoxy group content can be controlled. In this case, theorder of contacting the chemicals, the amount of the compound (c1) andthe reaction temperature of the compound (e) are essential.

The amount of the supported titanium is preferably 1.0% by weight ormore. The reason therefor is that when the amount of the supportedtitanium is less than 1.0% by weight, the activity per the catalyst issometimes decreased even if the activity per titanium is high (even ifthe RO/Ti is low).

Further, the amount of the supported titanium is more preferably 1.2% byweight or more, still more preferably 1.5% by weight or more.

The amount of the supported titanium can be controlled when thecomponent (a1) having the specific composition is selected or when thecatalyst is prepared under the specific reaction conditions. In thiscase, with regard to the component (a1), the composition of the oxideand the content of the magnesium compound are considered to beessential. With regard to the reaction conditions, the reactiontemperature of the compound (e) and the washing temperature after thereaction of the compound (e) are essential.

Method of Preparing Solid Catalyst Component [A2]

The method of the solid catalyst component [A2] can be a method in whichthe oxide (a2) of at least one element of the Groups II to IV elements,the oxide supporting the above alkoxy-group-containing magnesiumcompound or the alcohol complex of the halogen-containing magnesiumcompound, and the predetermined amount of the halogen-containing siliconcompound (b2) are brought into contact, and reacted, with each other,the reaction mixture is brought into contact, and reacted, with theelectron-donating compound (c2) and the halogen-containing titaniumcompound (d2) at a temperature of 120° C. or higher but 150° C. orlower, the reaction mixture is washed with an inert solvent, and thehalogen-containing titanium compound (d2) is reacted with the reactionproduct again (at least once) at a temperature of 120° C. or higher but150° C. or lower. The order of other contacts is not critical.

Preferably, the halogen-containing titanium compound (d2) is broughtinto contact with a reaction mixture obtained by bringing the compound(a2) and the halogen-containing silicon compound (b2) into contact witheach other, and then the electron-donating compound (c2) is brought intocontact with the reaction mixture, since the solid catalyst component inthis case can be sometimes improved in polymerization activity.

Further, these components may be brought into contact in the presence ofan inert solvent such as a hydrocarbon, or each component may be dilutedwith an inert solvent such as a hydrocarbon before they are brought intocontact. The inert solvent can be selected from those explained withregard to the preparation of the solid catalyst component [A1].

The amount of the above halogen-containing titanium compound (d2) permole of magnesium of the above alkoxy-group-containing magnesiumcompound or the alcohol complex of the halogen-containing magnesiumcompound is generally 0.5 to 100 mol, preferably 1 to 50 mol. When theabove molar ratio is outside the above range, the catalyst activity issometimes insufficient.

Further, the amount of the electron-donating compound (c2) per mole ofmagnesium of the above alkoxy-group-containing magnesium compound or thealcohol complex of the halogen-containing magnesium compound isgenerally 0.01 to 10 mol, preferably 0.05 to 1.0 mol. When the abovemolar ratio is outside the above range, the catalyst activity issometimes insufficient or an olefin polymer sometimes has insufficientstereoregularity.

The halogen-containing silicon compound (b2) is used in such an amountthat the molar ratio of the halogen to the magnesium of thealkoxy-group-containing magnesium compound or the alcohol complex of thehalogen-containing magnesium compound is generally 0.20 or more,preferably from 0.4 to 4.0, more preferably from 1.0 to 2.5. When theabove amount is much smaller than the above range, the catalyst activityor the effect on improvement in stereoregularity is not fully exhibited,and a formed polymer is caused to have an increased amount of a finepowder and a decreased bulk density. When it is too large, there isproduced no further effect on these improvements.

After the above compounds (a2) to (d2) are all added, they are broughtinto contact and allowed to react preferably in a temperature range of120 to 150° C., particularly preferably 125 to 140° C. When the abovecontact temperature is outside the above range, the catalyst activity orthe effect on improvement in stereoregularity is sometimes not fullyexhibited. The contact time period, the pressure during the contactingand the stirring during the contacting procedures are as explained withregard to the solid catalyst component [A1]. These contact conditionsare also applicable to the contact reaction that is carried out for thesecond time or more with the halogen-containing titanium compound (d2).

When a solvent is used in the contact procedures of thehalogen-containing titanium compound (d2), the amount of the solvent permole of the halogen-containing titanium compound (d2) is generally 5,000milliliters or less, preferably 10 to 1,000 milliliters. When the aboveratio is outside the above range, the uniformity of the contact or thecontact efficiency is sometimes degraded.

Further, after the first contact reaction of the halogen-containingtitanium compound (d2), it is sometimes desirable to wash the reactionmixture with an inert solvent at a temperature of 100 to 150° C.,particularly preferably 120 to 140° C. When the above washingtemperature is outside the above range, the catalyst activity or theeffect on improvement in stereoregularity is sometimes not fullyexhibited. The inert solvent can be selected from those explained in thepreparation of the solid catalyst component [A1].

After the contact reaction that is carried out for the second time andthereafter with the halogen-containing titanium compound (d2), thewashing temperature, the washing method, the amount of the inertsolvent, the washing time period, the number of times of the washing,the washing pressure and the stirring during the washing procedure areas explained with regard to the preparation of the solid catalystcomponent [A1]. The thus-obtained solid catalyst component [A2] can bestored in a dry state or in an inert solvent such as a hydrocarbon.

In the above-obtained solid catalyst component [A2], the molar ratio(RO/Ti) of the residual alkoxy group content (RO) to the supportedtitanium (Ti) is preferably 0.70 or less. That is because when the molarratio exceeds 0.70, no intended catalyst may be obtained.

Further, the above molar ratio is preferably 0.50 or less, morepreferably 0.45 or less.

Further, the residual alkoxy group content (RO) is preferably 0.50mmol/g or less. The reason therefor is that when the residual alkoxygroup content exceeds 0.50 mmol/g, the catalyst activity is low, thecatalyst cost increases, and the amount of catalyst residues such as C1,etc., in a powder increases, so that a product quality is sometimesdegraded.

Further, the residual alkoxy group content is more preferably 0.35mmol/g or less, still more preferably 0.20 mmol/g or less.

When the catalyst is prepared under the specific conditions, theresidual alkoxy group content can be controlled. In this case,particularly, the contact order of the compounds (a2) to (d2), theamount of the compound (b2) and the reaction temperature of the compound(d2) are essential.

Further, the amount of the supported titanium is preferably 1.0% byweight or more. The reason therefor is that when the amount of thesupported titanium is less than 1.0% by weight, the activity per thecatalyst is sometimes low even if the activity per titanium is high(even if the RO/Ti is low).

Further, the amount of the supported titanium is more preferably 1.2% byweight or more, still more preferably 1.5% by weight or more.

The amount of the supported titanium can be controlled when thecomponent (a2) having the specific composition is selected or when thecatalyst is prepared under the specific reaction conditions. In thiscase, with regard to the component (a2), the composition of the oxide,the content of the magnesium compound and the like are considered to beessential. With regard to the reaction conditions, the reactiontemperature of the compound (d2) and the washing temperature after thereaction of the compound (d2) are essential.

Method of Preparing Solid Catalyst Component [A3]

In the method of preparing the solid catalyst component [A3], the abovehalogen-containing titanium compound (a3), the alkoxy-group-containingmagnesium compound (b3), the halogen-containing silicon compound (c3)and optionally the electron-donating compound (d3) are allowed to react.

The method of preparing the solid catalyst component [A3] is preferablya method in which the above halogen-containing titanium compound (a3),the alkoxy-group-containing magnesium compound (b3), thehalogen-containing silicon compound (c3) and optionally theelectron-donating compound (d3) are allowed to react at a temperature of120° C. or higher but 150° C. or lower, the reaction mixture is washedwith an inert solvent, the halogen-containing titanium compound (a3) isfurther reacted with the reaction product at least once at a temperatureof 120° C. or higher but 150° C. or lower, and the reaction product iswashed with an inert solvent. In this case, the compound (c3) is ahalogen-containing silicon compound (c3-1) in which the molar ratio ofhalogen to the alkoxy group in the compound (b3) is 0.50 or more.

As described above, the compounds (a3) to (c3) or the compounds (a3) to(d3) are allowed to react at the specific temperature and then thehalogen-containing titanium compound (a3) is reacted with the reactionmixture again (at least once) at the specific temperature, whereby apolymer activity may be improved.

Other contact orders are not critical. For example, the above componentsmay be allowed to react in the presence of an inert solvent such as ahydrocarbon, or each component may be diluted with an inert solvent suchas a hydrocarbon beforehand. The inert solvent can be selected fromthose inert solvents explained with regard to the preparation of thesolid catalyst component [A1].

While the order of contact of the compounds (a3) to (c3) or thecompounds (a3) to (d3) is not specially limited, preferably, thealkoxy-group-containing magnesium compound (b3) and thehalogen-containing silicon compound (c3) are first brought into contactwith each other, then, the halogen-containing titanium compound (a3) isbrought into contact, the electron-donating compound (d3) is finallybrought into contact, and the halogen-containing titanium compound (a3)is further brought into contact, since the polymerization activity inthis case can be improved.

The amount of the halogen-containing titanium compound (a3) per mole ofmagnesium of the alkoxy-group-containing magnesium compound (b3) isgenerally 0.5 to 100 mol, preferably 1 to 50 mol. When the above molarratio is outside the above range, the catalyst activity may be sometimesinsufficient.

The amount of the electron-donating compound (d3) per mole of magnesiumof the alkoxy-group-containing magnesium compound (b3) is generally 0.01to 10 mol, preferably 0.05 to 1.0 mol. When the above molar ratio isoutside the above range, the catalyst activity or the stereoregularitymay be sometimes insufficient.

The halogen-containing silicon compound (c3) is used in such an amountthat the molar ratio of the halogen to the alkoxy group of thealkoxy-group-containing magnesium compound (b3) is 0.50 or more,preferably 0.60 to 4.0, more preferably 1.0 to 2.5. When the aboveamount is much smaller than the above range, the catalyst activity orthe effect on improvement in stereoregularity is not fully exhibited,and a formed polymer is caused to have an increased amount of a finepowder and a decreased bulk density. Even when the above amount is toolarge, there is no further effect produced on these improvements.

After the above compounds (a3) to (c3) or the compounds (a3) to (d3) areall added, they are brought into contact and reacted preferably in atemperature range of 120 to 150° C., particularly preferably 125 to 140°C. When the contact temperature is outside the above range, the catalystactivity or the effect on improvement in stereoregularity is sometimesnot fully exhibited. The contact time period, the pressure during thecontacting and the stirring during the contacting procedures are asexplained with regard to the preparation of the solid catalyst component[A1]. These contact conditions are also applicable to the contactreaction that is carried out with the halogen-containing titaniumcompound (a3) for the second time or more.

When a solvent is used in the contact procedure of thehalogen-containing titanium compound (a3), the amount of the solvent permole of the halogen-containing titanium compound (a3) is generally 5,000milliliters or less, preferably 10 to 1,000 milliliters. When the aboveratio is outside the above range, the contact uniformity and the contactefficiency may be degraded.

Concerning the temperature for the washing with an inert solvent afterthe contact reaction of the above halogen-containing titanium compound(a3), it is preferred to carry out the washing with the inert solvent ata temperature of 100 to 150° C., particularly preferably 120 to 140° C.,after the first contact reaction of the halogen-containing titaniumcompound (a3), since a larger effect is sometimes produced onimprovements in the catalyst activity and stereoregularity in this case.The above inert solvent can be selected from those inert solventsexplained with regard to the preparation of the solid catalyst component[A1].

Further, after the contact reaction that is carried out for the secondtime or more with the halogen-containing titanium compound (a3), thewashing temperature, the washing method, the amount of the inertsolvent, the washing time period, the number of times of the washing,the washing pressure and the stirring during the washing are asexplained with regard to the preparation of the solid catalyst component[A1]. The thus-obtained solid catalyst component [A3] can be stored in adry state or in an inert solvent such as a hydrocarbon.

In the above-obtained solid catalyst component [A3], preferably, themolar ratio of the residual alkoxy group to the supported titanium is0.30 or less.

Further, the above molar ratio is more preferably 0.20 or less, stillmore preferably 0.15 or less.

The residual alkoxy group content (RO) is preferably 0.13 mmol/g orless. The reason therefor is that when the residual alkoxy group contentexceeds 0.13 mmol/g, the polymerization activity is low, the catalystcost increases and the content of catalyst residues such as C1, etc., ina powder increases, so that the product quality is sometimes degraded.

Further, the residual alkoxy group content is more preferably 0.10mmol/g, still more preferably 0.08 mmol/g.

Further, the amount of the supported titanium is preferably 1.5% byweight or more. The reason therefor is that when the amount of thesupported titanium is less than 1.5% by weight, the activity per thecatalyst is sometimes low even if the activity per titanium is high(even if the RO/Ti is low).

Further, the amount of the supported titanium is more preferably 1.8% byweight or more, still more preferably 2.0% by weight or more.

When the electron-donating compound (d3) is used for preparing the solidcatalyst component [A3], it is easier to satisfy the above preferredvalues with regard to the molar ratio, the residual alkoxy content andthe amount of the supported titanium.

Further, the residual alkoxy group content can be controlled when thespecific support is selected as such or when the catalyst preparationconditions are controlled.

The amount of the supported titanium can be controlled when the catalystpreparation conditions, particularly, the reaction temperature of thecompound (a3) with each component and the temperature for the washingafter the reaction of the compound (a3) are set at the specifictemperatures.

Method of Preparing Solid Catalyst Component [A4]

The method of preparing the solid catalyst component [A4] is a method inwhich the above halogen-containing titanium compound (a4), thealkoxy-group-containing magnesium compound (b4) and optionally, theelectron-donating compound (c4) are allowed to react in the presence ofan aromatic hydrocarbon solvent.

In a preferred embodiment of the preparation method, thehalogen-containing titanium compound (a4), the alkoxy-group-containingmagnesium compound (b4) and optionally, the electron-donating compound(c4) are allowed to react in the presence of an aromatic hydrocarbonsolvent at a temperature of 120° C. or higher but 150° C. or lower, thereaction mixture is washed with an inert solvent, the halogen-containingtitanium compound (a4) is allowed to react further at least once at atemperature of 120° C. or higher but 150° C. or lower and the reactionproduct is washed with an inert solvent.

As described above, the compounds (a4) to (c4) are brought into contactand reacted at the specific temperature and then the halogen-containingtitanium compound (a4) is again (at least once) brought into contact andreacted at the specific temperature, whereby the polymer activity can beimproved.

Further, it is preferred to bring the electron-donating compound (c4)into contact after the halogen-containing titanium compound (a4) and thealkoxy-group-containing magnesium compound (b4) are brought into contactwith an aromatic hydrocarbon solvent, since the polymerization activityin this case can be improved.

Any aromatic hydrocarbon solvent can be used so long as it is in aliquid state at room temperature. Examples thereof include benzene,toluene, xylene, ethylbenzene, propylbenzene and trimethylbenzene. Ofthese, toluene, xylene and ethylbenzene are preferred.

The amount of the halogen-containing titanium compound (a4) per mole ofmagnesium of the above alkoxy-group-containing magnesium compound (b4)is generally 0.5 to 100 mol, preferably 1 to 50 mol. When the abovemolar ratio is outside the above range, the catalyst activity issometimes insufficient.

Further, the amount of the electron-donating compound (c4) per mole ofmagnesium of the above alkoxy-group-containing magnesium compound (b4)is generally 0.01 to 10 mol, preferably 0.05 to 1.0 mol. When the abovemolar ratio is outside the above range, the catalyst activity or thestereoregularity is sometimes insufficient.

The solvent for use in the above first reaction for supporting thehalogen-containing titanium compound (a4) is essentially an aromatichydrocarbon. When the above solvent is replaced, for example, with analiphatic or alicyclic hydrocarbon such as octane, decane orethylcyclohexane or halogenated hydrocarbon such as chlorobenzene,tetrachloroethane or chlorofluorocarbon, no sufficient performances canbe attained with regard to the polymerization activity, and the like.

After the above compounds (a4) and (b4) or the above compounds (a4) to(c4) are all added, they are brought into contact and reacted preferablyin the temperature range of 120 to 150° C., particularly preferably 125to 140° C. The above contact temperature is outside the above range, thecatalyst activity or the effect on improvement in stereoregularity issometimes not fully exhibited. The contact time period, the pressureduring the contact and the stirring during the contact procedures are asexplained with regard to the preparation of the solid catalyst component[A1]. These contact conditions are also applicable to the contactreaction that is carried out for the second time or more with regard tothe halogen-containing titanium compound (a).

In the procedure of bringing the halogen-containing titanium compound(a) into contact, the amount of the aromatic hydrocarbon solvent permole of the halogen-containing titanium compound (a) is generally 5,000milliliters or less, preferably 10 to 1,000 milliliters. When the abovemolar ratio is outside the above range, the contact uniformity or thecontact efficiency may be degraded.

After the first contact reaction of the halogen-containing titaniumcompound (a4), the reaction product from the contact reaction of theabove halogen-containing titanium compound (a4) is washed with an inertsolvent preferably at a temperature of 100 to 150° C., particularlypreferably 120 to 140° C., whereby the catalyst activity or the effecton improvement in stereoregularity is sometimes improved. The aboveinert solvent can be selected from those inert solvents explained withregard to the preparation of the solid catalyst component [A1].

Further, after the contact reaction that is carried out with thehalogen-containing titanium compound (a4) for the second time or more,the washing temperature, the washing method, the amount of the inertsolvent, the washing time period, the number of times of washing, thewashing pressure and the stirring during the washing are as explainedwith regard to the preparation of the solid catalyst component [A1]. Thethus-obtained solid catalyst component [A4] can be stored in a dry stateor in an inert solvent such as a hydrocarbon.

In the above-obtained solid catalyst component [A4], the molar ratio(RO/Ti) of the residual alkoxy group content (RO) to the supportedtitanium (Ti) is preferably 0.25 or less.

The above molar ratio is more preferably 0.15 or less, still morepreferably 0.13 or less.

Further, the residual alkoxy group content (RO) is preferably 0.15mmol/g or less. The reason therefor is that when the residual alkoxygroup content exceeds 0.15 mmol/g, the polymerization activity is low,the catalyst cost is increased, and the amount of catalyst residues suchas C1, etc., in a powder increases, so that the product quality issometimes degraded.

Further, the residual alkoxy group content is more preferably 0.09mmol/g or less, still more preferably 0.07 mmol/g or less.

Further, the amount of the supported titanium is preferably 1.5% byweight or more. The reason therefor is that when the amount of thesupported titanium is less than 1.5% by weight, the activity per thecatalyst is sometimes low even if the activity per titanium is high(even if the RO/Ti is low).

Further, the amount of the supported titanium is more preferably 1.8% byweight or more, still more preferably 2.0% by weight or more.

When the electron-donating compound (c4) is used for preparing the solidcatalyst component [A4], it is easier to satisfy the above preferredvalues with regard to the molar ratio, the residual alkoxy content andthe amount of the supported titanium.

Further, the residual alkoxy group content can be controlled when thespecific support is used or when the catalyst preparation conditions areset at the specific conditions.

The amount of the supported titanium can be controlled when the catalystpreparation conditions, particularly, the reaction temperature of thecompound (a4) with each component and the temperature for the washingafter the reaction of the compound (a4) are set at the specifictemperatures.

3. Process for Producing Olefin Polymer

Concerning the amount of each of the catalysts for olefinpolymerization, provided by the present invention, each of the solidcatalyst components [A1] to [A4] is used in such an amount that thetitanium atom amount per liter of a reaction volume is generally in therange of 0.00005 to 1 mmol.

The organic aluminum compound [B] is used in such an amount that thealuminum/titanium (atomic ratio) is generally in the range of 1 to1,000, preferably 10 to 500. When the above atomic ratio is outside theabove range, the catalyst activity is sometimes insufficient.

Further, the electron-donating compound [C] is used in such an amountthat the [C]/[B] (molar ratio) is generally in the range of 0.001 to5.0, preferably 0.01 to 2.0, more preferably 0.05 to 1.0. When the abovemolar ratio is outside the above range, the sufficient catalyst activityor the stereoregularity sometimes cannot be obtained. When a preliminarypolymerization is carried out, however, the amount of theelectron-donating compound [C] can be further decreased.

The olefin for use in the present invention is preferably an α-olefin ofthe following general formula (IV).R⁵—CH═CH₂   (IV)

In the above general formula (IV), R⁵ is a hydrogen atom or ahydrocarbon group, and the hydrocarbon group may be saturated orunsaturated, may be linear or branched, or may be cyclic. Specificexamples of the olefin include ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene,4-methyl-1-pentene, vinylcyclohexane, butadiene, isoprene, piperylene,and the like. These olefins may be used solely, or two or more olefinsof these may be used in combination. Of the above olefins, ethylene andpropylene are particularly preferred.

In the polymerization of an olefin in the present invention, thepreliminary polymerization of an olefin may be carried out as requiredbefore the regular polymerization thereof in view of the catalystactivity during the polymerization and the stereoregularity and powerform of an olefin polymer. In this case, the preliminary polymerizationof an olefin is carried out in the presence of a catalyst that is amixture of predetermined amounts of one of the solid catalyst components[A1] to [A4], the organic aluminum compound [B] and optionally theelectron-donating compound [C] generally in the temperature range of 1to 100° C. under a pressure of atmospheric pressure to approximately 5MPa, and then the main polymerization of the olefin is carried out inthe presence of the catalyst and the preliminary polymerization product.

In the polymerization procedure of the above main polymerization, anyone of solution polymerization, slurry polymerization, gaseous phasepolymerization, bulk polymerization, etc., can be employed. Further, anyone a batch method polymerization and a continuous polymerization can beemployed, and there can be employed two-step polymerization ormulti-step polymerization that is carried out under differentconditions.

Concerning the reaction conditions, further, the polymerization pressuretherefor is generally selected from the range of atmospheric pressure to8 MPa, preferably 0.2 to 5 MPa, and the polymerization temperature isgenerally selected from the range of 0 to 200° C., preferably 30 to 100°C., as required in view of polymerization activity. Although differingdepending upon olefins and the polymerization temperature, thepolymerization time period is generally 5 minutes to 20 hours,preferably approximately 10 minutes to 10 hours.

The molecular weight of an olefin polymer can be adjusted by adding achain transfer agent, preferably, hydrogen. Further, an inert gas suchas nitrogen may be present. Further, as far as the catalyst component inthe present invention is concerned, there may be employed a constitutionin which one of the solid catalyst components [A1] to [A4], the organicaluminum compound [B] and the electron-donating compound [C] are mixedin predetermined amounts, and immediately thereafter, an olefin isintroduced for polymerization. Alternatively, there may be employed aconstitution in which the above mixture is aged for approximately 0.2 to3 hours after the contact, and then an olefin is introduced forpolymerization. Further, the above catalyst component may be suspendedin an inert solvent, an olefin, or the like and fed. In the presentinvention, the post treatment after the polymerization can be carriedout according to a conventional method. That is, in a gaseous phasepolymerization method, a nitrogen current may be allowed to pass throughparticles of a polymer powder introduced out of a polymerizer after thepolymerization, for removing an olefin contained therein. Further, apolymer may be pelletized with an extruder as required, and in thiscase, a small amount of water, an alcohol or the like may be added fordeactivating the catalyst completely. In a bulk polymerization method, apolymer that is withdrawn from a polymerizer after the polymerizationcan be pelletized after a monomer is completely separated from thepolymer.

In the present invention, preferably, the residual C1 content in anolefin polymer obtained in the presence of the catalyst for olefinpolymerization is 35 ppm or less. The reason therefor is that when theresidual C1 content exceeds 35 ppm, not only the neutralizer costincreases, but also it sometimes induces the corrosion of a mold andfoaming during molding and the formation of a foreign matter.

The residual C1 content is more preferably 30 ppm or less, still morepreferably 25 ppm or less.

EXAMPLES

The present invention will be explained with reference to Exampleshereinafter, while the present invention shall not be limited to thefollowing Examples. Average particle diameters (D50) of oxides (a1) and(a2) and alkoxy-group-containing magnesium compounds (b3) and (b4),residual alkoxy group contents in solid catalyst components, amounts ofsupported Ti, bulk densities, average particle diameters (D50) and fineand coarse powder amounts of polymer powders and intrinsic viscosities[η], stereoregularity [mmmm] and C1 contents of polymers were determinedas follows.

(1) Average particle diameters (D50) of oxides (a1) and (a2) andcompounds (b3) and (b4): An oxide (a1) or (a2) or a compound (b3) or(b4) was suspended in a hydrocarbon solvent and measured by a lighttransmission method. A particle diameter distribution obtained by theabove method was plotted on a logarithmic-normal probability paper, anda 50% particle diameter was determined as an average particle diameter.

(2) Residual alkoxy group content of solid catalyst component: A solidcatalyst component was fully dried, accurately weighed, hermeticallycharged into a vial and fully hydrolyzed with 1.2 N hydrochloric acid.Then, an insoluble was filtered off, a filtrate was measured for analcohol content by gas chromatography, and a corresponding residualalkoxy content was calculated.

(3) Amount of supported Ti of solid catalyst component: A solid catalystcomponent was fully dried, then accurately weighed and fully hydrolyzedwith 3N sulfuric acid. Then, an insoluble was filtered off, andphosphoric acid as a masking agent was added to a filtrate. Further, a3% hydrogen peroxide aqueous solution was added to develop a color. Thethus-prepared solution was measured for an absorbance at 420nm by FT-IR,to determine a Ti concentration, and the amount of supported Ti of thesolid catalyst component was calculated.

(4) Bulk density of polymer powder: Measured according to JIS K 6721.

(5) Average particle diameter (D50), fine powder amount and coarsepowder amount of polymer powder: A particle diameter distributionmeasured with sieves was plotted on a logarithmic-normal probabilitypaper, and a 50% particle diameter was used as an average particlediameter. Further, a weight percentage of a powder passing through amesh opening size of 250 μm or less was defined as a fine powder amount,a weight percentage of a powder not passing through a mesh opening sizeof 2,830 μm or greater was defined as a coarse powder amount, and thesepercentages were determined.

(6) Intrinsic viscosity [η] of polymer: A polymer was dissolved indecalin and measured at 135° C.

(7) Stereoregularity of polymer [mmmm]:

A polymer was dissolved in a solution of a1,2,4-trichlorobenzene/heavy-benzene mixture having a ratio of 90:10(volume ratio), and the stereoregularity of a polymer was quantitativelydetermined on the basis of signals of methyl groups measured with a13C-NMR (trade name: LA-500, manufactured by JEOL Ltd.) at 130° C. by aproton complete decoupling method.

An isotactic pentad fraction [mmmm] refers to an isotactic fraction inpentad units of a polypropylene molecule chain, proposed by A. Zambelli,et al., in Macromolecules, Vol. 6, page 925 (1973) and determined on thebasis of 13C-NMR spectrum.

Further, a method of determining assignment of peaks of 13C-NMR spectrumwas according to the assignment proposed by A. Zambelli, et al., inMacromolecules, Vol. 8, page 687 (1975).

(8) C1 content in polymer: A sample was hot-pressed to prepare a plate,and the C1 content was quantitatively determined by a fluorescence X-rayanalysis method.

Example 1

(1) Preparation of Oxide of Element of Group II to IV Elements, theOxide Supporting Alcohol-Free Halogen-Containing Magnesium Compound

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then, 200 milliliters of dehydrated heptane, 40 g ofsilica gel (Si: 0.666 mmol) having an average particle diameter D50 of50 μm, a specific surface area of 300 m²/g and a pore volume of 1.6cm³/g and 0.166 mmol of butyloctylmagnesium were mixed and heated at 90°C. for 1.5 hours. Then, the mixture was cooled to 20° C., and a hydrogenchloride gas (1.66 mmol) was allowed to pass to carry out chlorinationfor 30 minutes. Then, the reaction product was washed with 200milliliters of dehydrated heptane three times at room temperature, andthe thus-obtained solid was analyzed for components to show that it hada magnesium content of 7.9 wt % and a chlorine content of 22.5 wt %(Cl/Mg molar ratio: 1.95).

(2) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then the flask was charged with 80 milliliters ofdehydrated octane and 16 g (Mg: 0.052 mol) of the silica supportsupporting magnesium chloride, prepared in the above (1). The mixturewas cooled to 5° C., 9.15 milliliters (0.156 mol) of dehydrated ethanolwas dropwise added over 15 minutes, and the mixture was heated at 80° C.for 1.5 hours. The resultant suspension was cooled to 40° C., 2.97milliliters (0.026 mol) of silicon tetrachloride was added, and themixture was stirred for 4 hours. Then, 77 milliliters (0.702 mol) oftitanium tetrachloride was dropwise added, the solution thereof wastemperature-increased to 65° C., and 1.39 milliliters (0.0052 mol) ofdi-n-butyl phthalate was added. Then, the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a contactingprocedure, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. To the remaining reaction product was added100 milliliters of dehydrated octane, and the mixture wastemperature-increased to 125° C. with stirring and maintained for 1minute. The stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times.Then, 122 milliliters (1.11 mol) of titanium tetrachloride was added,the mixture was stirred at an internal temperature of 125° C. for 2hours to carry out a contacting procedure, and the above washing withdehydrated octane at 125° C. was carried out 7 times, to give a solidcatalyst component. Table 1 shows the evaluation results thereof.

(3) Propylene Polymerization

An autoclave made of stainless steel with a stirrer, having an internalvolume of 1 liter, was fully dried and then subjected to replacement ofan atmosphere therein with nitrogen, and then the autoclave was chargedwith 400 milliliters of dehydrated heptane at room temperature. Theautoclave was further charged with 2.0 mmol of triethylaluminum, 0.25mmol of dicyclopentyldimethoxysilane and 0.0025 mmol, as Ti atom, of thesolid catalyst component prepared in the above (2), and hydrogen wasintroduced up to 0.1 MPa. Then, while propylene was introduced, theautoclave was temperature-increased to 80° C. and pressure-increased toa total pressure of 0.8 MPa, followed by polymerization for 1 hour.Then, the temperature and the pressure in the autoclave were decreased,and the reaction product was taken out and poured into 2 liters ofmethanol to deactivate the catalyst. The product was separated byfiltration and vacuum-dried to give a polypropylene. Table 1 shows theevaluation results thereof.

Example 2

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example1 except that the temperature for the washing with the octane after thetitanium-tetrachloride-supporting reaction carried out for the secondtime in Example 1(2) was changed to room temperature, and thethus-obtained solid catalyst component was evaluated. Table 1 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 1 except thatthe procedures in Example 1(3) were modified so that thedicyclopentyldimethoxysilane was replaced with 0.5 mmol ofcyclohexylmethyldimethoxysilane, that 0.005 mmol, as Ti atom, of thesolid catalyst component prepared in the above (1) was added and thathydrogen was introduced up to 0.05 MPa. The thus-obtained polypropylenewas evaluated. Table 1 shows the results.

Example 3

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then the flask was charged with 80 milliliters ofdehydrated octane and 16 g (Mg: 0.052 mol) of themagnesium-chloride-supporting silica support prepared in Example 1(1).The mixture was cooled to 5° C., 9.15 milliliters (0.156 mol) ofdehydrated ethanol was dropwise added over 15 minute, and the mixturewas heated at 80° C. for 1.5 hours. The resultant suspension was cooledto 40° C., 2.97 milliliters (0.026 mol) of silicon tetrachloride wasadded, the mixture was stirred for 4 hours, and then 77 milliliters(0.702 mol) of titanium tetrachloride was dropwise added. The resultantsolution was temperature-increased up to 65° C., and 1.39 milliliters(0.0052 mol) of di-n-butyl phthalate was added. Then, the mixture wasstirred at an internal temperature of 125° C. for 1 hour to carry out acontacting procedure. The stirring was stopped to precipitate a solid,and a supernatant was withdrawn. To the remaining reaction product wasadded 100 milliliters of dehydrated octane, and the mixture wastemperature-increased to 125° C. with stirring and maintained for 1minute. The stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times.Then, 122 milliliters (1.11 mol) of titanium tetrachloride was added,the mixture was stirred at an internal temperature of 125° C. for 2hours to carry out a contacting procedure, and the above washing withdehydrated octane at 125° C. was repeated 7 times. Further, 122milliliters (1.11 mol) of titanium tetrachloride was added, the mixturewas stirred at an internal temperature of 125° C. for 2 hours to carryout a contacting procedure, and the above washing with dehydrated octaneat 125° C. was repeated 7 times. The thus-obtained solid catalystcomponent was evaluated. Table 1 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 1 except thatthe solid catalyst component prepared in the above (1) was used inExample 1(3). The thus-obtained polypropylene was evaluated. Table 1shows the results.

Example 4

(1) Preparation of Solid Catalyst Component

A solid catalyst component was prepared in the same manner as in Example1 except that the procedures in Example 1(2) were modified so that theoctane was replaced with decane and that the temperatures for thesupporting reaction and the washing were changed to 135° C. Thethus-obtained solid catalyst component was evaluated. Table 1 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 1 except thatthe solid catalyst component prepared in the above (1) was used inExample 1(2). The thus-obtained polypropylene was evaluated. Table 1shows the results.

Comparative Example 1

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g (Mg: 0.052 mol) of the magnesium-chloride-supporting silicasupport prepared in Example 1(1). The mixture was cooled to 5° C., 9.15milliliters (0.156 mol) of dehydrated ethanol was dropwise added over 15minutes, and the mixture was heated at 80° C. for 1.5 hours. Theresultant suspension was cooled to 70° C., and 1.39 milliliters (0.0052mol) of di-n-butyl phthalate was added. The resultant solution wastemperature-increased up to 80° C., then, 77 milliliters (0.70 mol) oftitanium tetrachloride was dropwise added, and the mixture was stirredat an internal temperature of 110° C. for 2 hours to carry out acontacting procedure. Then, the stirring was stopped to precipitate asolid, and a supernatant was withdrawn. To the remaining reactionmixture was added 100 milliliter of dehydrated heptane, and the mixturewas temperature-increased up to 90° C. with stirring and maintained for1 minute. The stirring was stopped to precipitate a solid, and asupernatant was withdrawn. The above washing procedure was repeated 7times. Then, 122 milliliters (1.11 mol) of titanium tetrachloride wasadded, the mixture was stirred at an internal temperature of 110° C. for2 hours to carry out a contacting procedure, the stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. Then, the abovewashing with heptane at 90° C. was repeated 7 times, and thethus-obtained solid catalyst component was evaluated. Table 1 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 1 except thatthe solid catalyst component prepared in the above (1) was used inExample 1(2). The thus-obtained polypropylene was evaluated. Table 1shows the results.

Comparative Example 2

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g (Mg: 0.052 mol) of the magnesium-chloride-supporting silicasupport prepared in Example 1(1). The mixture was cooled to 5° C., 9.15milliliters (0.156 mol) of dehydrated ethanol was dropwise added over 15minutes, and the mixture was heated at 80° C. for 1.5 hours. Theresultant suspension was cooled to 40° C., 0.89 milliliters (0.0078 mol)of silicon tetrachloride was added and the mixture was stirred for 40minutes. The mixture was temperature-increased up to 70° C., then, 1.39milliliters (0.0052 mol) of di-n-butyl phthalate was added. Theresultant solution was temperature-increased up to 80° C., then, 77milliliters (0.70 mol) of titanium tetrachloride was dropwise added, themixture was stirred at an internal temperature of 110° C. for 2 hours,to carry out a contacting procedure. Then, the stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. To the remainingreaction mixture was added 100 milliliters of dehydrated heptane, andthe mixture was temperature-increased up to 90° C. with stirring andmaintained for 1 minute. Then, the stirring was stopped to precipitate asolid, and a supernatant was withdrawn. The above washing procedure wasrepeated 7 times. Then, 122 milliliters (1.11 mol) of titaniumtetrachloride was added, the mixture was stirred at an internaltemperature of 110° C. for 2 hours to carry out a contacting procedure,the stirring was stopped to precipitate a solid, and a supernatant waswithdrawn. Then, the above washing procedure at 90° C. with heptane wasrepeated 7 times, and the thus-obtained solid catalyst component wasevaluated. Table 1 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 1 except thatthe solid catalyst component prepared in the above (1) was used inExample 1(2). The thus-obtained polypropylene was evaluated. Table 1shows the results.

As is clearly shown in Table, according to Examples, the solid catalystcomponents have high polymerization activity, and there can be obtainedolefin polymers whose residual C1 content is small and which areexcellent in stereoregularity and a powder form. TABLE 1 ComparativeComparative Unit Example 1 Example 2 Example 3 Example 4 Example 1Example 2 Compound Mg content (wt %) 7.9 7.9 7.9 7.9 7.9 7.9 (a1) Clcontent (wt %) 23.0 23.0 23.0 23.0 23.0 23.0 D₅₀ (μm) 50 50 50 50 50 50Catalyst Reaction temperature (° C.) 125 125 125 135 110 110 Washingtemperature* (° C.) 125 125→r.t. 125 135 90 90 EtOH/Mg (molar ratio) 3.03.0 3.0 3.0 3.0 3.0 SiCl₄/Mg (molar ratio) 0.5 0.5 0.5 0.5 0 0.15 Numberof times of supporting 2 2 3 2 2 2 Order of contacting* OH→Si→ OH→Si→OH→Si→ OH→Si→ OH→ID→Ti OH→Si→ Ti→ID Ti→ID Ti→ID Ti→ID ID→Ti Residualalkoxy group content (mmol/g) 0.132 0.145 0.117 0.134 0.533 0.461 Amountof supported Ti (mmol/g) 0.401 0.660 0.376 0.395 0.710 0.668 Alkoxygroup/Ti (molar ratio) 0.33 0.22 0.31 0.34 0.75 0.69 Amount of supportedTi (wt %) 1.92 3.16 1.80 1.89 3.40 3.20 Olefin Polymerization activity(kg/g-Ti) 540 310 600 540 130 150 polymer Polymerization activity(kg/g-Cat) 10.4 9.8 10.8 10.2 4.4 4.8 Cl content (ppm) 20 25 19 21 47 43[η] (dL/g) 1.21 1.29 1.24 1.27 1.26 1.26 Stereoregularity (mol %) 99.698.1 99.5 99.5 99.0 99.2 D₅₀ (μm) 980 890 1020 960 550 570 Fine powderamount(<250 μm) (wt %) 3.0 3.4 2.8 3.1 7.5 5.3 Coarse powder (wt %) 0.30.4 0.3 0.5 1.0 0.4 amount(>2830 μm) Bulk density (g/mL) 0.41 0.40 0.420.40 0.34 0.37Washing temperature:r.t.: room temperatureOrder of contacting:OH: ethanol (compound (b1),Si: silicon tetrachloride (compound (c1)),ID: internal donor (compound (d1)),Ti: titanium tetrachloride (compound (e))

Example 5

(1) Preparation of Solid Oxide Supporting Alkoxy-Group-ContainingMagnesium Compound

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and 200 milliliters of dehydrated heptane, 40 g (667 mmol)of silica gel having an average particle diameter D50 of 50 μm, aspecific surface area of 300 m²/g and a pore volume of 1.6 cm³/g andbutylethylmagnesium (222 mmol) were mixed, followed by heating at 90° C.for 1.5 hours. Then, the reaction mixture was cooled to 5° C., 28.6milliliters (489 mmol) of ethanol was dropwise added, and the mixturewas heated at 80° C. for 1 hour. Then, the reaction product was washedwith 200 milliliter of dehydrated heptane at room temperature 3 times,and the thus-obtained solid was analyzed for a composition to show thatit had a magnesium content of 6.9 wt % and an ethoxy content of 23.7 wt% (OEt/Mg molar ratio: 1.85).

(2) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas and charged with 80 milliliters of dehydrated octane and 16g (Mg: 45.4 mmol) of the silica support supporting magnesium ethoxideprepared in the above (1). At 40° C., 2.60 milliliters (22.7 mmol) ofsilicon tetrachloride was dropwise added, and the mixture was stirredfor 4 hours. Then, 77 milliliters (702 mmol) of titanium tetrachloridewas dropwise added, the resultant solution was temperature-increased upto 65° C., and then 1.21 milliliters (4.54 mmol) of di-n-butyl phthalatewas added. Then, the mixture was stirred at an internal temperature of125° C. for 1 hour to carry out a contacting procedure, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. To theremaining reaction mixture was added 100 milliliters of dehydratedoctane, and the mixture was temperature-increased up to 125° C. withstirring and maintained for 1 minute. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. The above washingprocedure was repeated 7 times. Then, 122 milliliters (1.11 mol) oftitanium tetrachloride was added, the mixture was stirred at an internaltemperature of 125° C. for 2 hours to carry out a contacting procedure,and then the above washing with dehydrated octane at 125° C. was carriedout 7 times to give a solid catalyst component. The thus-obtained solidcatalyst component was evaluated. Table 2 shows the results.

(3) Propylene Polymerization

An autoclave made of stainless steel with a stirrer, having an internalvolume of 1 liter, was fully dried and then subjected to replacement ofan atmosphere therein with nitrogen, and then the autoclave was chargedwith 400 milliliters of dehydrated heptane at room temperature. Theautoclave was further charged with 2.0 mmol of triethylaluminum, 0.25mmol of dicyclopentyldimethoxysilane and 0.0025 mmol, as Ti atom, of thesolid catalyst component prepared in the above (2), and hydrogen wasintroduced up to 0.1 MPa. Then, while propylene was introduced, theautoclave was temperature-increased to 80° C. and pressure-increased toa total pressure of 0.8 MPa, followed by polymerization for 1 hour.

Then, the temperature and the pressure in the autoclave were decreased,and the reaction product was taken out and poured into 2 liters ofmethanol to deactivate the catalyst. The product was separated byfiltration and vacuum-dried to give a polypropylene. Table 1 shows theevaluation results thereof.

Example 6

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example5 except that the temperature for the washing with the octane after thetitanium-tetrachloride-supporting reaction carried out for the secondtime in Example 5(2) was changed to room temperature, and thethus-obtained solid catalyst component was evaluated. Table 2 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 5 except thatthe procedures in Example 5(3) were modified so that thedicyclopentyldimethoxysilane was replaced with 0.5 mmol ofcyclohexylmethyldimethoxysilane, that 0.005 mmol, as Ti atom, of thesolid catalyst component prepared in the above (1) was added and thathydrogen was introduced up to 0.05 MPa. The thus-obtained polypropylenewas evaluated. Table 2 shows the results.

Example 7

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas and charged with 80 milliliters of dehydrated octane and 16g (Mg: 45.4 mmol) of the silica support supporting magnesium ethoxideprepared in Example 5(1). At 40° C., 2.60 milliliters (22.7 mmol) ofsilicon tetrachloride was dropwise added, and the mixture was stirredfor 4 hours. Then, 77 milliliters (702 mmol) of titanium tetrachloridewas dropwise added, the resultant solution was temperature-increased upto 65° C., and then 1.21 milliliters (4.54 mmol) of di-n-butyl phthalatewas added. Then, the mixture was stirred at an internal temperature of125° C. for 1 hour to carry out a contacting procedure, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. To theremaining reaction mixture was added 100 milliliters of dehydratedoctane, and the mixture was temperature-increased up to 125° C. withstirring and maintained for 1 minute. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. The above washingprocedure was repeated 7 times. Then, 122 milliliters (1.11 mol) oftitanium tetrachloride was added, the mixture was stirred at an internaltemperature of 125° C. for 2 hours to carry out a contacting procedure,and then the above washing with dehydrated octane at 125° C. wasrepeated 7 times. Further, 122 milliliters (1.11 mol) of titaniumtetrachloride was added, the mixture was stirred at an internaltemperature of 125° C. for 2 hours to carry out a contacting procedure,and then the above washing with dehydrated octane at 125° C. wasrepeated 7 times, to give a solid catalyst component. The thus-obtainedsolid catalyst component was evaluated. Table 2 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 5 except thatthe solid catalyst component prepared in the above (1) was used inExample 5(3). The thus-obtained polypropylene was evaluated. Table 2shows the results.

Example 8

(1) Preparation of Solid Catalyst Component

A solid catalyst component was prepared in the same manner as in Example5 except that the procedures in Example 5(2) were modified so that theoctane was replaced with decane as preparation and washing solvent andthat the reaction temperature and the washing temperature were changedto 135° C. The thus-obtained solid catalyst component was evaluated.Table 2 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 5 except thatthe solid catalyst component prepared in the above (1) was used inExample 5(3). The thus-obtained polypropylene was evaluated. Table 2shows the results.

Example 9

(1) Preparation of Solid Oxide Supporting Alcohol Complex ofHalogen-Containing Magnesium Compound

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, then, 12.7 g (133 mmol) of magnesium chloride wassuspended in 127 milliliters of heptane, 73.4 milliliters (800 mmol) ofbutanol was dropwise added at 40° C., and the mixture was heated at 98C.for 1 hour. Then, the reaction mixture was cooled to 70° C., 40 g (667mmol) of silica gel having an average particle diameter D50 of 50 μm, aspecific surface area of 300 m²/g and a pore volume of 1.6 cm³/g wasadded, the mixture was stirred for 0.5 hour. Further, the reactionproduct was washed with 200 milliliters of dehydrated heptane at roomtemperature 3 times, and the thus-obtained solid component was analyzedto show that it had a magnesium content of 4.0 wt %, a chlorine contentof 11.3 wt % and a butoxy group content of 39.1 wt % (Cl/Mg molar ratio:1.93, OBu/Mg molar ratio: 3.25).

(2) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas and charged with 80 milliliters of dehydrated octane and 16g (Mg: 26.3 mmol) of the silica support supporting the butanol complexof magnesium chloride prepared in the above (1). At 40° C., 1.51milliliters (13.2 mmol) of silicon tetrachloride was dropwise added, andthe mixture was stirred for 4 hours. Then, 77 milliliters (702 mmol) oftitanium tetrachloride was dropwise added, the resultant solution wastemperature-increased up to 65° C., and then 0.70 milliliters (2.63mmol) of di-n-butyl phthalate was added. Then, the mixture was stirredat an internal temperature of 125° C. for 1 hour to carry out acontacting procedure, the stirring was stopped to precipitate a solid,and a supernatant was withdrawn. To the remaining reaction mixture wasadded 100 milliliters of dehydrated octane, and the mixture wastemperature-increased up to 125° C. with stirring and maintained for 1minute. The stirring was stopped to precipitate a solid, and asupernatant was withdrawn. The above washing procedure was repeated 7times. Then, 122 milliliters (1.11 mol) of titanium tetrachloride wasadded, the mixture was stirred at an internal temperature of 125° C. for2 hours to carry out a contacting procedure, and then the above washingwith dehydrated octane at 125° C. was carried out 7 times to give asolid catalyst component. The thus-obtained solid catalyst component wasevaluated. Table 2 shows the results.

(3) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 5 except thatthe solid catalyst component prepared in the above (2) was used inExample 5(3). The thus-obtained polypropylene was evaluated. Table 2shows the results.

Comparative Example 3

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g (Mg: 45.4 mmol) of the magnesium-ethoxide-supporting silicasupport prepared in Example 5(1). At 40° C., 2.60 milliliters (22.7mmol) of silicon tetrachloride was dropwise added, and the mixture wasstirred for 4 hours. Then, 77 milliliters (702 mmol) of titaniumtetrachloride was dropwise added, the resultant solution wastemperature-increased up to 65° C., and then 1.21 milliliters (4.54mmol) of di-n-butyl phthalate was added. Then, the mixture was stirredat an internal temperature of 125° C. for 1 hour to carry out acontacting procedure, the stirring was stopped to precipitate a solid,and a supernatant was withdrawn. Further, 100 milliliters of dehydratedoctane was added, and the mixture was stirred at room temperature. Thestirring was stopped to precipitate a solid, and a supernatant waswithdrawn. This washing procedure was repeated 7 times, and thethus-obtained solid catalyst component was evaluated. Table 2 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 5 except thatthe solid catalyst component prepared in the above (1) was used inExample 5(3). The thus-obtained polypropylene was evaluated. Table 2shows the results.

Comparative Example 4

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated heptanand 16 g (Mg: 45.4 mmol) of the magnesium-ethoxide-supporting silicasupport prepared in Example 5(1). The mixture was heated up to 70° C.,and 1.21 milliliters (4.54 mmol) of di-n-butyl phthalate was added. Theresultant solution was temperature-increased up to 80° C., then, 77milliliters (702 mmol) of titanium tetrachloride was dropwise added, andthe mixture was stirred at an internal temperature of 110° C. for 2hours to carry out a contacting procedure. Then, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. To theremaining reaction mixture was added 100 milliliters of dehydratedheptan, and the mixture was temperature-increased up to 90° C. withstirring and maintained for 1 minute. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. This washingprocedure was repeated 7 times. Then, 122 milliliters (1.11 mol) oftitanium tetrachloride was added, the mixture was stirred at an internaltemperature of 110° C. for 2 hours to carry out a contacting procedure,the stirring was stopped to precipitate a solid, and a supernatant waswithdrawn. Then, the above washing with heptane at 90° C. was repeated 7times, and the thus-obtained solid catalyst component was evaluated.Table 2 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 5 except thatthe solid catalyst component prepared in the above (1) was used inExample 5(3). The thus-obtained polypropylene was evaluated. Table 2shows the results.

As is clearly shown in Table, according to Examples, the solid catalystcomponents have high polymerization activity, and there can be obtainedolefin polymers whose residual C1 content is small and which areexcellent in stereoregularity and a powder form. TABLE 2 ComparativeComparative Unit Example 5 Example 6 Example 7 Example 8 Example 9Example 3 Example 4 Oxide Mg content (wt %) 6.9 6.9 6.9 6.9 4.0 6.9 6.9(a2) OR content (wt %) 23.7 23.7 23.7 23.7 39.1 23.7 23.7 OR/Mg (molarratio) 1.85 1.85 1.85 1.85 3.25 1.85 1.85 D₅₀ (μm) 50 50 50 50 50 50 50Catalyst Reaction temperature (° C.) 125 125 125 135 125 125 110 Washingtemperature* (° C.) 125 125→r.t. 125 135 125 r.t. 90 SiCl₄/Mg (molarratio) 0.5 0.5 0.5 0.5 0.5 0.5 0 Number of times 2 2 3 2 2 1 2 ofsupporting Order of contacting* Si→Ti→ID Si→Ti→ID Si→Ti→ID Si→Ti→IDSi→Ti→ID Si→ID→Ti ID→Ti Residual alkoxy (mmol/g) 0.178 0.158 0.162 0.1850.182 0.573 0.583 group content Amount of supported Ti (mmol/g) 0.4450.689 0.426 0.451 0.434 0.699 0.747 Alkoxy group/Ti (molar ratio) 0.400.23 0.38 0.41 0.42 0.82 0.78 Amount of supported Ti (wt %) 2.13 3.302.04 2.16 2.08 3.35 3.58 Olefin Polymerization activity (kg/g-Ti) 430270 480 420 390 90 110 polymer Polymerization activity (kg/g-Cat) 9.28.9 9.8 9.1 8.1 3.0 3.9 Cl content (ppm) 23 27 21 23 25 84 65 [η] (dL/g)1.25 1.26 1.27 1.23 1.29 1.12 1.18 Stereoregularity (mol %) 99.5 98.199.6 99.5 99.5 98.4 98.9 D₅₀ (μm) 860 830 900 870 810 390 440 Finepowder (wt %) 3.2 3.6 2.8 3.4 3.3 6.0 5.8 amount(<250 μm) Coarse powder(wt %) 0.3 0.4 0.3 0.3 0.3 0.5 0.4 amount(>2830 μm) Bulk density (g/mL)0.40 0.39 0.41 0.40 0.38 0.35 0.36Washing temperature:r.t.: room temperatureOrder of contacting:Si: silicon tetrachloride (compound (b2))ID: internal donor (compound (c2))Ti: titanium tetrachloride (compound (d2))

Example 10

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g of diethoxymagnesium (prepared by reacting metal magnesium,ethanol and iodine at an iodine/Mg gram atom ratio of 0.0057 at areaction temperature of 50° C.; D50: 35 μm). The mixture was heated to40° C., 8.0 milliliters of silicon tetrachloride (halogen/alkoxy group:1.0) was added, the mixture was stirred for 4 hours, and then 3.4milliliters of di-n-butyl phthalate was added. The resultant solutionwas temperature-increased up to 65° C., then, 77 milliliters of titaniumtetrachloride was dropwise added, and the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a contactingprocedure. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. To the remaining reaction mixture was added100 milliliters of dehydrated octane, and the mixture wastemperature-increased up to 125° C. with stirring and maintained for 1minute. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. The above washing procedure was repeated 7times. Then, 122 milliliters of titanium tetrachloride was added, themixture was stirred at an internal temperature of 125° C. for 2 hours tocarry out a contacting procedure, and then the above washing withdehydrated octane at 125° C. was carried out 6 times to give a solidcatalyst component. Table 3 shows the evaluation results thereof.

(2) Propylene Polymerization

An autoclave made of stainless steel with a stirrer, having an internalvolume of 1 liter, was fully dried and subjected to replacement of anatmosphere therein with nitrogen, and then the autoclave was chargedwith 400 milliliters of dehydrated heptane at room temperature. Theautoclave was further charged with 2.0 mmol of triethylaluminum, 0.25mmol of dicyclopentyldimethoxysilane and 0.0025 mmol, as Ti atom, of thesolid catalyst component prepared in the above (1), and hydrogen wasintroduced up to 0.1 MPa. Then, while propylene was introduced, theautoclave was temperature-increased to 80° C. and pressure-increased toa total pressure of 0.8 MPa, followed by polymerization for 1 hour.

Then, the temperature and the pressure in the autoclave were decreased,and the reaction product was taken out and poured into 2 liters ofmethanol to deactivate the catalyst. The product was separated byfiltration and vacuum-dried to give a polypropylene. Table 3 shows theevaluation results thereof.

Example 11

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10 except that the temperature for the washing with the octane after thetitanium-tetrachloride-supporting reaction carried out for the secondtime in Example 10(1) was changed to room temperature, and thethus-obtained solid catalyst component was evaluated. Table 3 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 10 exceptthat the procedures in Example 10(2) were modified so that thedicyclopentyldimethoxysilane was replaced with 0.5 mmol ofcyclohexylmethyldimethoxysilane, that 0.005 mmol, as Ti atom, of thesolid catalyst component prepared in the above (1) was added and thathydrogen was introduced up to 0.05 MPa. The thus-obtained polypropylenewas evaluated. Table 3 shows the results.

Example 12

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10 except that diethoxymagnesium having an average particle diameter(D50) of 10 μm, which was obtained at an iodine/Mg gram atomic ratio of0.00019 at a reaction temperature of 50° C., was used. The thus-obtainedsolid catalyst component was evaluated. Table 3 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 10 exceptthat the solid catalyst component prepared in the above (1) was used inExample 10(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Example 13

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example10 except that diethoxymagnesium having an average particle diameter(D50) of 70 μm, which was obtained at an iodine/Mg gram atomic ratio of0.019 at a reaction temperature of 78° C., was used in Example 10 (1).The thus-obtained solid catalyst component was evaluated. Table 3 showsthe results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 10 exceptthat the solid catalyst component prepared in the above (1) was used inExample 10(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Example 14

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g of diethoxymagnesium (prepared by reacting metal magnesium,ethanol and iodine at an iodine/Mg gram atom ratio of 0.019 at areaction temperature of 78° C., D50: 70 μm). The mixture was heated to40° C., and 8.0 milliliters of silicon tetrachloride (halogen/alkoxygroup: 1.0) was added. The mixture was stirred for 4 hours, and then 47milliliters of titanium tetrachloride was dropwise added. The resultantsolution was temperature-increased up to 65° C., 3.4 milliliters ofdi-n-butyl phthalate was added, and the mixture wastemperature-increased up to 125° C. Then, the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a contactingprocedure. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. To the remaining reaction mixture was added100 milliliters of dehydrated octane, and the mixture wastemperature-increased up to 125° C. with stirring and maintained for 1minute. The stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times.Then, 77 milliliters of titanium tetrachloride was added, and themixture was stirred at an internal temperature of 125° C. for 2 hours tocarry out a contacting procedure. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. Further, 100milliliters of dehydrated octane was added, and the mixture was stirredat room temperature. The stirring was stopped to precipitate a solid,and a supernatant was withdrawn. This washing procedure was repeated 7times, to give a solid catalyst component. Table 3 shows the evaluationresults thereof.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 11 exceptthat the solid catalyst component prepared in the above (1) was used inExample 11(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Example 15

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g of diethoxymagnesium (prepared by reacting metal magnesium,ethanol and iodine at an iodine/Mg gram atom ratio of 0.019 at areaction temperature of 78° C., D50: 70 μm). The mixture was heated to40° C., and 8.0 milliliters of silicon tetrachloride (halogen/alkoxygroup: 1.0) was added. The mixture was stirred for 4 hours, and then 3.4milliliters of di-n-butyl phthalate was added. The resultant solutionwas temperature-increased up to 65° C., and 47 milliliters of titaniumtetrachloride was dropwise added, and the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a contactingprocedure. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. To the remaining reaction mixture was added100 milliliters of dehydrated octane, and the mixture wastemperature-increased up to 125° C. with stirring and maintained for 1minute. The stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times.Then, 77 milliliters of titanium tetrachloride was added, and themixture was stirred at an internal temperature of 125° C. for 2 hours tocarry out a contacting procedure. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. Further, 100milliliters of dehydrated octane was added, and the mixture was stirredat room temperature. The stirring was stopped to precipitate a solid,and a supernatant was withdrawn. This washing procedure was repeated 7times, to give a solid catalyst component. Table 3 shows the evaluationresults thereof.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 11 exceptthat the solid catalyst component prepared in the above (1) was used inExample 11(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Example 16

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g of diethoxymagnesium (prepared by reacting metal magnesium,ethanol and iodine at an iodine/Mg gram atom ratio of 0.019 at areaction temperature of 78° C., D50: 70 μm). The mixture was heated to40° C., and 8.0 milliliters of silicon tetrachloride (halogen/alkoxygroup: 1.0) was added. The mixture was stirred for 4 hours, and then 3.4milliliters of di-n-butyl phthalate was added, and the mixture wastemperature-increased up to 65° C. Then, 47 milliliter of titaniumtetrachloride was dropwise added, and the mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a contactingprocedure. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. To the remaining reaction mixture was added100 milliliters of dehydrated octane, and the mixture wastemperature-increased up to 125° C. with stirring and maintained for 1minute. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times.Then, 77 milliliters of titanium tetrachloride was added, and themixture was stirred at an internal temperature of 125° C. for 1 hour tocarry out a contacting procedure. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. The above washingwith dehydrated octane at 125° C. was repeated 7 times. Further, 77milliliters of titanium tetrachloride was added again, and the mixturewas stirred at an internal temperature of 125° C. for 2 hours to carryout a contacting procedure. Then, the stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. Further, 100milliliters of dehydrated octane was added, and the mixture was stirredat room temperature. The stirring was stopped to precipitate a solid,and a supernatant was withdrawn. This washing procedure was repeated 7times to give a solid catalyst component. Table 3 shows the evaluationresults thereof.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 11 exceptthat the solid catalyst component prepared in the above (1) was used inExample 11(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Comparative Example 5

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g of diethoxymagnesium (prepared by reacting metal magnesium,ethanol and iodine at an iodine/Mg gram atom ratio of 0.019 at areaction temperature of 78° C., D50: 70 μm). The mixture was heated to40° C., and 8.0 milliliters of silicon tetrachloride (halogen/alkoxygroup: 1.0) was added. The mixture was stirred for 4 hours, and then 3.4milliliters of di-n-butyl phthalate was added. The resultant solutionwas temperature-increased up to 65° C., and then 47 milliliter oftitanium tetrachloride was dropwise added. The mixture was stirred at aninternal temperature of 125° C. for 1 hour to carry out a contactingprocedure. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. Further, 100 milliliters of dehydrated octanewas added, and the mixture was stirred at room temperature. The stirringwas stopped to precipitate a solid, and a supernatant was withdrawn.This washing procedure was repeated 7 times to give a solid catalystcomponent. Table 3 shows the evaluation results thereof.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 11 exceptthat the solid catalyst component prepared in the above (1) was used inExample 11(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Comparative Example 6

(1) Preparation of Solid Catalyst Component

A solid catalyst component was prepared in the same manner as in Example14 except that the step of treatment with silicon tetrachloride inExample 14(1) was omitted. The thus-obtained solid catalyst componentwas evaluated. Table 3 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 11 exceptthat the solid catalyst component prepared in the above (1) was used inExample 11(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Comparative Example 7

(1) Preparation of Solid Catalyst Component

A solid catalyst component was prepared in the same manner as in Example14 except that 0.8 milliliter of silicon tetrachloride (halogen/alkoxygroup: 0.10) was used in Example 14(1). The thus-obtained solid catalystcomponent was evaluated. Table 3 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 11 exceptthat the solid catalyst component prepared in the above (1) was used inExample 11(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Comparative Example 8

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g of diethoxymagnesium (prepared by reacting metal magnesium,ethanol and iodine at an iodine/Mg gram atom ratio of 0.019 at areaction temperature of 78° C., D50: 70 μm). The mixture was heated to50° C., and 4.8 milliliters of silicon tetrachloride (halogen/alkoxygroup: 0.60) was added. The mixture was stirred for 20 minutes, and then2.5 milliliters of diethyl phthalate was added. The resultant solutionwas temperature-increased up to 70° C., and then 47 milliliter oftitanium tetrachloride was dropwise added. The mixture was stirred at aninternal temperature of 110° C. for 2 hours to carry out a contactingprocedure. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. To the remaining reaction mixture was added100 milliliters of dehydrated octane, and the mixture wastemperature-increased up to 90° C. with stirring and maintained for 1minute. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times.Then, 77 milliliters of titanium tetrachloride was added, and themixture was stirred at an internal temperature of 110° C. for 2 hours tocarry out a contacting procedure. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. Then, 100milliliters of dehydrated octane was added, and the mixture was stirredat room temperature. The stirring was stopped to precipitate a solid,and a supernatant was withdrawn. This washing procedure was repeated 7times to give a solid catalyst component. Table 3 shows the evaluationresults thereof.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 11 exceptthat the solid catalyst component prepared in the above (1) was used inExample 11(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Comparative Example 9

(1) Preparation of Solid Catalyst Component

A solid catalyst component was prepared in the same manner as inComparative Example 6 except that a support prepared by synthesizingdiethoxymagnesium having an average particle diameter (D50) of 540 μm ata reaction temperature of 78° C. without using iodine and pulverizingthe diethoxymagnesium with a ball mill for 24 hours was used inComparative Example 6(1). The thus-obtained solid catalyst component wasevaluated. Table 3 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 11 exceptthat the solid catalyst component prepared in the above (1) was used inExample 11(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

Comparative Example 10

(1) Preparation of Solid Catalyst Component

A solid catalyst component was prepared in the same manner as in Example13 except that 2.4 milliliters of silicon tetrachloride (halogen/alkoxygroup: 0.30) was used in Example 13(1). The thus-obtained solid catalystcomponent was evaluated. Table 3 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 10 exceptthat the solid catalyst component prepared in the above (1) was used inExample 10(2). The thus-obtained polypropylene was evaluated. Table 3shows the results.

As is clearly shown in Table, according to Examples, the solid catalystcomponents have high polymerization activity, and there can be obtainedolefin polymers excellent in powder form. TABLE 3 Example ExampleExample Example Example Example Example Unit 10 11 12 13 14 15 16Compound Initiator I₂ I₂ I₂ I₂ I₂ I₂ I₂ (b3) species X₂ or YX/Mg (Gram0.0057 0.0057 0.00019 0.019 0.019 0.019 0.019 atom ratio) Reaction (°C.) 50 50 50 78 78 78 78 temperature Average particle (μm) 35 35 10 7070 70 70 diameter (D₅₀) Catalyst Reaction (° C.) 125 125 125 125 125 125125 temperature Washing (° C.) 125 125→r.t. 125 125 125→r.t. 125→r.t.125→r.t. temperature* Halogen/ (molar 1.0 1.0 1.0 1.0 1.0 1.0 1.0 alkoxygroup ratio) Number of times 2 2 2 2 2 2 3 of supporting Order ofSi→ID→Ti Si→ID→Ti Si→ID→Ti Si→ID→Ti Si→Ti→ID Si→ID→Ti Si→ID→Ticontacting* Residual alkoxy (mmol/g) 0.049 0.058 0.045 0.087 0.109 0.1090.076 group content Amount of (mmol/g) 0.340 0.564 0.411 0.334 0.6180.511 0.507 supported Ti Alkoxy group/ (molar 0.14 0.10 0.11 0.26 0.180.18 0.15 Ti ratio) Amount of (wt %) 1.63 2.70 1.97 1.60 2.96 2.45 2.43supported Ti Internal DNBP DNBP DNBP DNBP DNBP DNBP DNBP donor* ExternalDCPDMS CHMDMS DCPDMS DCPDMS CHMDMS CHMDMS CHMDMS donor* OlefinPolymerization (kg/g-Ti) 1470 600 1350 750 470 400 420 polymer activityPolymerization (kg/g-Cat) 23.9 16.1 26.6 12.0 13.9 9.8 10.2 activity [η](dL/g) 1.54 1.25 1.40 1.46 1.27 1.17 1.21 Stereoregularity (mol %) 99.798.0 99.5 99.5 98.0 98.1 98.1 Average particle (μm) 610 590 200 14001420 1230 1280 diameter(D₅₀) Fine powder (wt %) 4.7 2.2 35.5 3.8 6.0 5.24.8 amount (<250 μm) Coarse powder (wt %) 1.6 1.3 0.2 0.4 0.1 0.4 0.5amount (>2830 μm) Bulk density (g/mL) 0.41 0.41 0.36 0.34 0.33 0.33 0.34Comparative Comparative Comparative Comparative Comparative ComparativeUnit Example 5 Example 6 Example 7 Example 8 Example 9 Example 10Compound Initiator I₂ I₂ I₂ I₂ — I₂ (b3) species X₂ or YX/Mg (Gram 0.0190.019 0.019 0.019 0 0.019 atom ratio) Reaction (° C.) 78 78 78 78 78 78temperature Average particle (μm) 70 70 70 70 540 70 diameter (D₅₀)Catalyst Reaction (° C.) 125 125 125 110 110 125 temperature Washing (°C.) r.t. 125→r.t. 125→r.t. 90→r.t. 90→r.t. 125 temperature* Halogen/(molar 1.0 0 0.10 0.60 0.60 0.30 alkoxy group ratio) Number of times 1 22 2 2 2 of supporting Order of Si→ID→Ti Ti→ID Si→Ti→ID Si→ID→Ti Si→ID→TiSi→ID→Ti contacting* Residual alkoxy (mmol/g) 0.369 0.266 0.222 0.1990.533 0.135 group content Amount of (mmol/g) 0.737 0.806 0.693 0.5850.751 0.386 supported Ti Alkoxy group/ (molar 0.50 0.33 0.32 0.34 0.710.35 Ti ratio) Amount of (wt %) 3.53 3.86 3.32 2.80 3.60 1.85 supportedTi Internal DNBP DNBP DNBP DEP DEP DNBP donor* External CHMDMS CHMDMSCHMDMS CHMDMS CHMDMS DCPDMS donor* Olefin Polymerization (kg/g-Ti) 170240 290 220 100 550 polymer activity Polymerization (kg/g-Cat) 6.0 9.39.6 6.2 3.6 10.2 activity [η] (dL/g) 1.10 1.20 1.23 1.19 1.08 1.35Stereoregularity (mol %) 96.6 97.4 97.6 96.8 96.3 99.2 Average particle(μm) 900 960 1050 1020 490 1200 diameter(D₅₀) Fine powder (wt %) 4.513.4 9.8 3.3 15.0 6.1 amount (<250 μm) Coarse powder (wt %) 1.0 3.8 2.00.8 2.0 1.2 amount (>2830 μm) Bulk density (g/mL) 0.31 0.26 0.29 0.310.25 0.31Washing temperature:r.t.: room temperatureOrder of contacting:Ti: titanium tetrachloride (compound (a3)),ID: Internal donor (compound (d3)),Si: Silicon tetrachloride(compound (c3))Internal donor species:DNBP: di-n-butyl phthalate,DEP: diethyl phthalateExternal donor species:DCPDMS: dicyclopentyldimethoxysilane,CHMDMS: cyclohexylmethyldimethoxysilane

Example 17

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 128 milliliters of dehydratedethylbenzene and 16 g of diethoxymagnesium (prepared by reacting metalmagnesium, ethanol and iodine at an iodine/Mg gram atom ratio of 0.0057at a reaction temperature of 50° C., D50: 35 μm). At 5° C., 64milliliters of titanium tetrachloride was dropwise added, the mixturewas temperature-increased up to 90° C., and then, 4.3 milliliters ofdi-n-butyl phthalate was added. The resultant solution was furthertemperature-increased and stirred at an internal temperature of 125° C.for 2 hours to carry out a contacting procedure. Then, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. To theremaining reaction mixture was added 240 milliliters of dehydratedethylbenzene, and the mixture was temperature-increased up to 125° C.with stirring and maintained for 1 minute. Then, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. Thiswashing procedure was repeated twice. Further, 96 milliliters ofdehydrated ethylbenzene and 64 milliliters of titanium tetrachloridewere added, and the mixture was stirred at an internal temperature of125° C. for 2 hours to carry out a contacting procedure. The stirringwas stopped to precipitate a solid, and a supernatant was withdrawn. Theabove washing procedure was repeated twice. Then, 100 milliliters ofdehydrated octane was added, and the mixture was temperature-increasedup to 125° C. with stirring and maintained for 1 minute. Then, thestirring was stopped to precipitate a solid, and a supernatant waswithdrawn. This washing procedure was repeated four times, and theresultant solid catalyst component was evaluated. Table 4 shows theresults.

(2) Propylene Polymerization

An autoclave made of stainless steel with a stirrer, having an internalvolume of 1 liter, was fully dried and subjected to replacement of anatmosphere therein with nitrogen, and then the autoclave was chargedwith 400 milliliters of dehydrated heptane at room temperature. Theautoclave was further charged with 2.0 mmol of triethylaluminum, 0.25mmol of dicyclopentyldimethoxysilane and 0.0025 mmol, as Ti atom, of thesolid catalyst component prepared in the above (1), and hydrogen wasintroduced up to 0.1 MPa. Then, while propylene was introduced, theautoclave was temperature-increased to 80° C. and pressure-increased toa total pressure of 0.8 MPa, followed by polymerization for 1 hour.Then, the temperature and the pressure in the autoclave were decreased,and the reaction product was taken out and poured into 2 liters ofmethanol to deactivate the catalyst. The product was separated byfiltration and vacuum-dried to give a polypropylene. Table 4 shows theevaluation results thereof.

Example 18

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example17 except that the temperature for the washing with the octane after thetitanium-tetrachloride-supporting reaction carried out for the secondtime in Example 17(1) was changed to room temperature, and thethus-obtained solid catalyst component was evaluated. Table 4 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 17 exceptthat the procedures in Example 17(2) were modified so that thedicyclopentyldimethoxysilane was replaced with 0.5 mmol ofcyclohexylmethyldimethoxysilane, that 0.005 mmol, as Ti atom, of thesolid catalyst component prepared in the above (1) was added and thathydrogen was introduced up to 0.05 MPa. The thus-obtained polypropylenewas evaluated. Table 4 shows the results.

Example 19

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example17 except that diethoxymagnesium having an average particle diameter(D50) of 10 μm, prepared at an iodine/Mg gram atom ratio of 0.00019 at areaction temperature of 50° C., was used in Example 17(1). Thethus-obtained solid catalyst component was evaluated. Table 4 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 17 exceptthat the solid catalyst component prepared in the above (1) was used inExample 17(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Example 20

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example17 except that diethoxymagnesium having an average particle diameter(D50) of 70 μm, prepared at an iodine/Mg gram atom ratio of 0.019 at areaction temperature of 78° C., was used In Example 17(1). Thethus-obtained solid catalyst component was evaluated. Table 4 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 17 exceptthat the solid catalyst component prepared in the above (1) was used inExample 17(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Example 21

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 128 milliliters of dehydratedp-xylene and 16 g of diethoxymagnesium (prepared by reacting metalmagnesium, ethanol and iodine at an iodine/Mg gram atom ratio of 0.019at a reaction temperature of 78° C., D50: 70 μm). At 5° C., 64milliliters of titanium tetrachloride was dropwise added, the mixturewas temperature-increased up to 90° C., and then 4.3 milliliters ofdi-n-butyl phthalate was added. The resultant solution was furthertemperature-increased and stirred at 130° C. for 2 hours to carry out acontacting procedure. Then, the stirring was stopped to precipitate asolid, and a supernatant was withdrawn. To the remaining reactionmixture was added 240 milliliters of dehydrated p-xylene, and themixture was temperature-increased up to 130° C. with stirring andmaintained for 1 minute. Then, the stirring was stopped to precipitate asolid, and a supernatant was withdrawn. This washing procedure wasrepeated twice. Further, 96 milliliters of dehydrated p-xylene and 64milliliters of titanium tetrachloride were added, and the mixture wasstirred at an internal temperature of 130° C. for 2 hours to carry out acontacting procedure. Then, the stirring was stopped to precipitate asolid, and a supernatant was withdrawn. The above washing procedure wascarried out twice. Then, 100 milliliters of dehydrated octane was added,and the mixture was temperature-increased up to 130° C. with stirringand maintained for 1 minute. Then, the stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. This washingprocedure was repeated four times. The thus-obtained solid catalystcomponent was evaluated. Table 4 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 17 exceptthat the solid catalyst component prepared in the above (1) was used inExample 17(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Example 22

(1) Preparation of Solid Catalyst Component

A solid catalyst component was obtained in the same manner as in Example17 except that the procedures in Example 17(1) were modified so thatdiethoxymagnesium having an average particle diameter (D50) of 70 μm,prepared at an iodine/Mg gram atom ratio of 0.019 at a reactiontemperature of 78° C., was used and that the temperature for the washingwith the octane after the titanium-tetrachloride-supporting reactioncarried out for the second time was changed to room temperature. Thethus-obtained solid catalyst component was evaluated. Table 4 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 17 exceptthat the solid catalyst component prepared in the above (1) was used inExample 17(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Example 23

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 128 milliliters of dehydratedethylbenzene and 16 g of diethoxymagnesium (prepared by reacting metalmagnesium, ethanol and iodine at an iodine/Mg gram atom ratio of 0.019at a reaction temperature of 78° C., D50: 70 μm). At 5° C., 64milliliters of titanium tetrachloride was dropwise added, the mixturewas temperature-increased up to 90° C., and then 4.3 milliliters ofdi-n-butyl phthalate was added. The resultant solution was furthertemperature-increased and stirred at an internal temperature of 125° C.for 2 hours to carry out a contacting procedure. Then, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. To theremaining reaction mixture was added 240 milliliters of dehydratedethylbenzene, and the mixture was temperature-increased up to 125° C.with stirring and maintained for 1 minute. Then, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. Thiswashing procedure was repeated twice. Then, 96 milliliters of dehydratedethylbenzene and 64 milliliters of titanium tetrachloride were added,and the mixture was stirred at an internal temperature of 125° C. for 2hours to carry out a contacting procedure. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. The above washingprocedure was carried out twice. Further, 96 milliliters of dehydratedethylbenzene and 64 milliliters of titanium tetrachloride were added,and the mixture was stirred at an internal temperature of 125° C. for 2hours to carry out a contacting procedure. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. The above washingprocedure was carried out twice. Then, 100 milliliters of dehydratedoctane was added, and the mixture was stirred at room temperature. Thestirring was stopped to precipitate a solid, and a supernatant waswithdrawn. This washing procedure was repeated four times. Thethus-obtained solid catalyst component was evaluated. Table 4 shows theresults.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 18 exceptthat the solid catalyst component prepared in the above (1) was used inExample 18(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Comparative Example 11

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 128 milliliters of dehydratedethylbenzene and 16 g of diethoxymagnesium (prepared by reacting metalmagnesium, ethanol and iodine at an iodine/Mg gram atom ratio of 0.019at a reaction temperature of 78° C., D50: 70 μm). At 5° C., 64milliliters of titanium tetrachloride was dropwise added, the mixturewas temperature-increased up to 90° C., and then 4.3 milliliters ofdi-n-butyl phthalate was added. The resultant solution was furthertemperature-increased and stirred at 125° C. for 2 hours to carry out acontacting procedure. Then, the stirring was stopped to precipitate asolid, and a supernatant was withdrawn. To the remaining reactionmixture was added 240 milliliters of dehydrated ethylbenzene, and themixture was temperature-increased up to 125° C. with stirring andmaintained for 1 minute. Then, the stirring was stopped to precipitate asolid, and a supernatant was withdrawn. This washing procedure wasrepeated twice. Further, 100 milliliters of dehydrated octane was added,and the mixture was stirred at room temperature. The stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. Thiswashing procedure was repeated four times. The thus-obtained solidcatalyst component was evaluated. Table 4 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 18 exceptthat the solid catalyst component prepared in the above (1) was used inExample 18(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Comparative Example 12

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g of diethoxymagnesium (prepared by reacting metal magnesium,ethanol and iodine at an iodine/Mg gram atom ratio of 0.019 at areaction temperature of 78° C., D50: 70 μm), and 47 milliliters oftitanium tetrachloride was dropwise added at 40° C. The resultantsolution was further temperature-increased up to 65° C., and 3.4milliliters of di-n-butyl phthalate was added. Then, the mixture wastemperature-increased up to 125° C. and then stirred at an internaltemperature of 125° C. for 1 hour to carry out a contacting procedure.Then, the stirring was stopped to precipitate a solid, and a supernatantwas withdrawn. To the remaining reaction mixture was added 100milliliters of dehydrated octane, and the mixture wastemperature-increased up to 125° C. with stirring and maintained for 1minute. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times.Then, 77 milliliters of titanium tetrachloride was added, and themixture was stirred at an internal temperature of 125° C. for 2 hours tocarry out a contacting procedure. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. Further, 100milliliters of dehydrated octane was added, and the mixture was stirredat room temperature. The stirring was stopped to precipitate a solid,and a supernatant was withdrawn. This washing procedure was repeated 7times. The thus-obtained solid catalyst component was evaluated. Table 4shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 18 exceptthat the solid catalyst component prepared in the above (1) was used inExample 18(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Comparative Example 13

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 80 milliliters of dehydrated octaneand 16 g of diethoxymagnesium (prepared by reacting metal magnesium,ethanol and iodine at an iodine/Mg gram atom ratio of 0.019 at areaction temperature of 78° C., DS0: 70 μm). The mixture was heated to50° C., and 2.4 milliliters of silicon tetrachloride was added. Themixture was stirred for 20 minutes, and then 2.5 milliliters of diethylphthalate was added. The resultant solution was temperature-increased upto 70° C., then, 47 milliliters of titanium tetrachloride was dropwiseadded, and the mixture was stirred at an internal temperature of 110° C.for 2 hours to carry out a contacting procedure. Then, the stirring wasstopped to precipitate a solid, a supernatant was withdrawn, 100milliliters of dehydrated octane was added, and the mixture wastemperature-increased up to 90° C. with stirring and maintained for 1minute. Then, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times.Then, 77 milliliters of titanium tetrachloride was added, and themixture was stirred at an internal temperature of 110° C. for 2 hours tocarry out a contacting procedure. The stirring was stopped toprecipitate a solid, and a supernatant was withdrawn. Then, 100milliliters of dehydrated octane was added, the mixture was stirred atroom temperature, the stirring was stopped to precipitate a solid, and asupernatant was withdrawn. This washing procedure was repeated 7 times,and the thus-obtained solid catalyst component was evaluated. Table 4shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 18 exceptthat the solid catalyst component prepared in the above (1) was used inExample 18(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Comparative Example 14

(1) Preparation of Solid Catalyst Component

A three-necked flask with a stirrer, having an internal volume of 0.5liter, was subjected to replacement of an atmosphere therein withnitrogen gas, and then charged with 128 milliliters of dehydratedethylbenzene and 16 g of diethoxymagnesium (prepared-by reacting metalmagnesium, ethanol and iodine at an iodine/Mg gram atom ratio of 0.019at a reaction temperature of 78° C., D50: 70 μm). At 5° C., 32milliliters of titanium tetrachloride was dropwise added, the mixturewas temperature-increased up to 90° C., and then 4.3 milliliters ofdi-n-butyl phthalate was added. The resultant solution wastemperature-increased and stirred at an internal temperature of 115° C.for 2 hours to carry out a contacting procedure. Then, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. To theremaining reaction mixture was added 160 milliliters of dehydratedethylbenzene, and the mixture was temperature-increased up to 115° C.with stirring and maintained for 1 minute. Then, the stirring wasstopped to precipitate a solid, and a supernatant was withdrawn. Thiswashing procedure was repeated twice. Further, 96 milliliters ofdehydrated ethylbenzene and 32 milliliters of titanium tetrachloridewere added, and the mixture was stirred at an internal temperature of115° C. for 2 hours to carry out a contacting procedure. The stirringwas stopped to precipitate a solid, and a supernatant was withdrawn.Then, 200 milliliters of dehydrated octane was added, the mixture wasstirred at room temperature, the stirring was stopped to precipitate asolid, and a supernatant was withdrawn. This washing procedure wasrepeated 10 times, and the thus-obtained solid catalyst component wasevaluated. Table 4 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 18 exceptthat the solid catalyst component prepared in the above (1) was used inExample 18(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

Comparative Example 15

(1) Preparation of Solid Catalyst Component

A solid catalyst component was prepared in the same manner as inComparative Example 14 except that a support prepared by synthesizingdiethoxymagnesium having an average particle diameter (D50) of 540 μm ata reaction temperature of 78° C. without using iodine and pulverizingthe diethoxymagnesium with a ball mill for 24 hours was used inComparative Example 14(1). The thus-obtained solid catalyst componentwas evaluated. Table 4 shows the results.

(2) Propylene Polymerization

Propylene was polymerized in the same manner as in Example 18 exceptthat the solid catalyst component prepared in the above (1) was used inExample 18(2). The thus-obtained polypropylene was evaluated. Table 4shows the results.

As is clearly shown in Table, according to Examples, the solid catalystcomponents have high polymerization activity, and there can be obtainedolefin polymers excellent in powder form. TABLE 4 Example ExampleExample Example Example Example Example Unit 17 18 19 20 21 22 23Compound Initiator species I₂ I₂ I₂ I₂ I₂ I₂ I₂ (b4) X₂ or YX/Mg (Gramatom 0.0057 0.0057 0.00019 0.019 0.019 0.019 0.019 ratio) Reactiontemperature (° C.) 50 50 50 78 78 78 78 D₅₀ (μm) 35 35 10 70 70 70 70Catalyst Temperature for (° C.) 125 125 125 125 130 125 125 supportingWashing temperature* (° C.) 125 125→r.t. 125 125 130 125→r.t. 125→r.t.Preparation solvent* EB EB EB EB XL EB EB Chlorinating agent — — — — — —— species Number of times 2 2 2 2 2 2 3 of supporting Order ofcontacting* Ti→ID Ti→ID Ti→ID Ti→ID Ti→ID Ti→ID Ti→ID Residual alkoxy(mmol/g) 0.048 0.065 0.063 0.114 0.100 0.146 0.098 group content Amountof (mmol/g) 0.484 0.727 0.528 0.520 0.501 0.695 0.574 supported TiAlkoxy group/Ti (molar ratio) 0.10 0.09 0.12 0.22 0.20 0.21 0.17 Amountof (wt %) 2.32 3.48 2.53 2.49 2.40 3.33 2.75 supported Ti OlefinPolymerization (kg/g-Ti) 1310 580 1360 820 830 390 450 polymer activityPolymerization (kg/g-Cat) 30.3 20.1 34.4 20.4 19.9 13.0 12.4 activity[η] (dL/g) 1.44 1.28 1.42 1.46 1.50 1.22 1.24 Stereoregularity (mol %)99.6 98.2 99.5 99.5 99.6 98.2 98.4 D₅₀ (μm) 730 600 760 1600 1610 14501400 Fine powder (wt %) 1.7 1.9 1.5 3.9 4.0 6.7 6.5 amount(<250 μm)Coarse powder (wt %) 1.7 1.5 1.9 0.5 0.4 0.3 0.4 amount(>2830 μm) Bulkdensity (g/mL) 0.40 0.41 0.36 0.35 0.34 0.33 0.34 ComparativeComparative Comparative Comparative Comparative Unit Example 11 Example12 Example 13 Example 14 Example 15 Compound Initiator species I₂ I₂ I₂I₂ — (b4) X₂ or YX/Mg (Gram atom 0.019 0.019 0.019 0.019 0 ratio)Reaction temperature (° C.) 78 78 78 78 78 D₅₀ (μm) 70 70 70 70 540Catalyst Temperature for (° C.) 125 125 110 115 115 supporting Washingtemperature* (° C.) 125→r.t. 125→r.t. 90→r.t. 115→r.t. 115→r.t.Preparation solvent* EB OC OC EB EB Chlorinating agent — — SiCl₄ — —species Number of times 1 2 2 2 2 of supporting Order of contacting*Ti→ID Ti→ID Si→ID→Ti Ti→ID Ti→ID Residual alkoxy (mmol/g) 0.277 0.2660.206 0.155 0.456 group content Amount of (mmol/g) 0.770 0.806 0.6050.553 0.760 supported Ti Alkoxy group/Ti (molar ratio) 0.36 0.33 0.340.28 0.60 Amount of (wt %) 3.69 3.86 2.90 2.65 3.64 supported Ti OlefinPolymerization (kg/g-Ti) 220 240 220 340 150 polymer activityPolymerization (kg/g-Cat) 8.1 9.3 6.3 9.0 5.5 activity [η] (dL/g) 1.111.20 1.19 1.13 1.18 Stereoregularity (mol %) 96.6 97.4 96.8 98.1 96.5D₅₀ (μm) 1180 960 1020 1030 610 Fine powder (wt %) 4.9 13.4 3.3 5.0 18.0amount(<250 μm) Coarse powder (wt %) 0.8 3.8 0.8 0.2 2.7 amount(>2830μm) Bulk density (g/mL) 0.31 0.26 0.31 0.36 0.28Contacting temperature:r.t.: room temperaturePreparation solvent:EB: ethylbenzene,XL: p-xylene,OC: octaneOrder of contacting:Ti: titanium tetrachloride (compound (a4)),ID: internal donor (compound (c4)),Si: silicon tetrachlorideIndustrial Utility

According to the present invention, there can be provided a solidcatalyst component and a solid catalyst for olefin polymerization whichhas high polymerization activity and can give an olefin polymer whoseresidual C1 content is small and which is excellent in stereoregularityand powder form, and a process for producing an olefin polymer.

1.-43. (canceled)
 44. A process for producing a solid catalyst component for olefin polymerization, comprising: reacting (a1) an oxide of at least one element that is selected from Group II to Group IV elements and that supports an alcohol-free halogen-containing magnesium compound with (b1) an alcohol at a hydroxyl group/magnesium molar ratio of 1.0 or more, and then with (c1) a halogen-containing silicon compound at a halogen/magnesium molar ratio of at least 0.20, reacting a reaction product from the compounds (a1), (b1) and (c1) with (d) an electron-containing compound and (e) a halogen-containing titanium compound at a temperature of at least 120° C. but no more than 150° C., and washing the resultant reaction mixture with an inert solvent to obtain a solid catalyst component.
 45. The process of claim 44, wherein the first washing with an inert solvent after the reaction of said compounds (a1) to (e) is carried out at a temperature of at least 100° C. but no more than 150° C.
 46. The process of claim 44, wherein the molar ratio (RO/Ti) of residual alkoxy groups (RO) to supported titanium (Ti) in the solid catalyst component is 0.50 or less.
 47. The process of claim 44, wherein said alcohol (b1) is ethanol.
 48. The process of claim 44, wherein said halogen-containing silicon compound (c1) is silicon tetrachloride.
 49. The process of claim 46, wherein said molar ratio (RO/Ti) is 0.45 or less.
 50. The process of claim 44, wherein the content of residual alkoxy group (RO) in the solid catalyst component is 0.40 mmol/g or less.
 51. The process of claim 44, wherein the amount of a supported-titanium in the solid catalyst component is at least 1.0% by weight.
 52. A process for producing a solid catalyst component for olefin polymerization, comprising; reacting (a2) an oxide of at least one element selected from the Group II to Group IV elements, the oxide supporting an alkoxy-group-containing magnesium compound or an alcohol complex of a halogen-containing magnesium compound and (b2-1) a halogen-containing silicon compound whose amount as a halogen/magnesium molar ratio is at least 0120 based on the oxide (a2) and (d2) a halogen-containing titanium compound at a temperature of at least 120° C. but no more than 150° C., washing the reaction product with an inert solvent, then, reacting compound (d2) again at a temperature of 120° C. but no more than 150° C., and washing the reaction product with an inert solvent to obtain a solid catalyst component.
 53. The process of claim 52, wherein the first washing with an inert solvent after the reaction of said compounds (a1) to (d2) is carried out at a temperature of 100° C. but no more than 150° C.
 54. The process of claim 52, wherein the molar ratio (RO/Ti) of residual alkoxy groups (RO) to supported titanium (Ti) in the solid catalyst component is 0.70 or less.
 55. The process of claim 52, wherein said halogen-containing silicon compound (b2-1) is silicon tetrachloride.
 56. The process of claim 54, wherein said molar ratio (RO/Ti) is 0.50 or less.
 57. The process of claim 52, wherein the content of residual alkoxy group (RO) is the solid catalyst component is 0.50 mmol/g or less.
 58. The process of claim 52, wherein the amount of a supported titanium in the solid catalyst component is at least 1.0% by weight.
 59. A process for producing a solid catalyst component for olefin polymerization, comprising; reacting (a3) a halogen-containing titanium compound, (b3) an alkoxy-group-containing magnesium compound, and (c3-1) a halogen-containing silicon compound in which the molar ratio of halogen to the alkoxy group of the alkoxy-group-containing magnesium compound (b3) is 0.50 or more, (d3) an electron-donating compound, or (a3) a halogen-containing titanium compound, (b3) an alkoxy-group-containing magnesium compound, and (c3-1) a halogen-containing silicon compound in which the molar ratio of halogen to the alkoxy group of the alkoxy-group-containing magnesium compound (b3) is 0.50 or more, at a temperature of 120° C. but no more than 150° C. to obtain a reaction mixture, washing the reaction mixture with an inert solvent, further reacting the reaction mixture with (a3) a halogen-containing titanium compound at least once at a temperature of 120° C. but no more than 150° C., and washing the reaction mixture with an inert solvent to obtain a solid catalyst component.
 60. The process of claim 59, wherein the first washing with an inert solvent after the reaction of said compounds (a1) to (d3) is carried out at a temperature of 100° C. but no more than 150° C.
 61. The process of claim 59, wherein the molar ratio (RO/Ti) of residual alkoxy groups (RO) to supported titanium (Ti) in the solid catalyst component is 0.30 or less.
 62. The process of claim 59, wherein said compound (b3) is a compound obtained by reacting metal magnesium, an alcohol and a halogen and/or halogen-containing compound containing at least 0.0001 gram atom of halogen atom per mole of said metal magnesium.
 63. The process of claim 62, wherein the metal magnesium, the alcohol and the halogen and/or halogen-containing compound are reacted at a temperature of 30 to 60° C.
 64. The process of claim 59, wherein said compound (b3) has an average particle diameter (D50) of no more than 50 μm.
 65. The process of claim 59, wherein said compound (b3) is dialkoxymagnesium.
 66. The process of claim 59, wherein said compound (c3-1) is silicon tetrachloride.
 67. The process of claim 61, wherein said molar ratio (RO/Ti) is 0.20 or less.
 68. The process of claim 59, wherein the content of residual alkoxy group (RL) in the solid catalyst component is 0.13 mmol/g or less.
 69. The process as recited in claim 59, wherein the amount of a supported-titanium in the solid catalyst component is at least 1.5% by weight.
 70. A process for producing a solid catalyst component for olefin polymerization, comprising: reacting (a4) a halogen-containing titanium compound, and (b4) an alkoxy-group-containing magnesium compound, or (a4) a halogen-containing titanium compound, (b4) an alkoxy-group-containing magnesium compound, and (c4) an electron-donating compound in the presence of an aromatic hydrocarbon solvent at a temperature of at least 120° C. but no more than 150° C. to obtain a reaction mixture, washing the reaction mixture with an inert solvent, further reacting the following halogen-containing titanium compound (a4) at least once at a temperature of at least 120° C. but 150° C. and washing the reaction product with an inert solvent to obtain a solid catalyst component.
 71. The process of claim 70, wherein the first washing with an inert solvent after the reaction of said compounds (a1) to (c4) is carried out at a temperature of 100° C. but no more than 150° C.
 72. The process of claim 70, wherein the molar ratio (RO/Ti) of residual alkoxy groups (RL) to supported titanium (Ti) in the solid catalyst component is 0.25 or less.
 73. The process of claim 70, wherein said compound (b4) is an alkoxy-group-containing magnesium compound obtained by reacting metal magnesium, an alcohol and a halogen and/or halogen-containing compound containing at least 0.0001 gram atom of halogen atom per mole of said metal magnesium.
 74. The process of claim 73, wherein said metal magnesium, said alcohol and said halogen and/or halogen-containing compound are reacted at a temperature of 30 to 60° C.
 75. The process of claim 70, wherein said compound (b4) is dialkoxymagnesium.
 76. The process of claim 70, wherein said compound (b4) has an average particle diameter (D50) of 50 μm or less.
 77. The process of claim 72, wherein said molar ratio (RO/Ti) is 0.15 or less.
 78. The process of claim 70, wherein the content of residual alkoxy group (RO) in the solid catalyst component is 0.15 mmol/g or less.
 79. The process of claim 70, wherein the amount of a supported-titanium in the solid catalyst component is 1.5% by weight or more. 